WO1999041193A1 - PROCEDE DE PRODUCTION DE LiPF6 PUR - Google Patents

PROCEDE DE PRODUCTION DE LiPF6 PUR Download PDF

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Publication number
WO1999041193A1
WO1999041193A1 PCT/EP1999/000141 EP9900141W WO9941193A1 WO 1999041193 A1 WO1999041193 A1 WO 1999041193A1 EP 9900141 W EP9900141 W EP 9900141W WO 9941193 A1 WO9941193 A1 WO 9941193A1
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WO
WIPO (PCT)
Prior art keywords
lipf
diethyl ether
lif
solution
reaction
Prior art date
Application number
PCT/EP1999/000141
Other languages
German (de)
English (en)
Inventor
Klaus Schade
Ulrich Wietelmann
Original Assignee
Metallgesellschaft Aktiengesellschaft
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Metallgesellschaft Aktiengesellschaft filed Critical Metallgesellschaft Aktiengesellschaft
Publication of WO1999041193A1 publication Critical patent/WO1999041193A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H01M6/166—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solute
    • 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 invention relates to a process for the production of pure lithium hexafluorophosphate, LiPF s , from LiF and PC1 S in diethyl ether.
  • LiPF s Lithium hexafluorophosphate
  • LiPF ⁇ is a moderately hydrolysis-sensitive substance that is extremely hygroscopic and releases hydrogen fluoride (HF) in contact with moist air.
  • HF hydrogen fluoride
  • HF has an extremely damaging effect on the cycle stability of lithium ion batteries, since it can detach metals from the cathodes consisting of transition metal oxides and thus cause the electrodes to decay.
  • the battery manufacturers therefore prefer the LiPF s in a form which is as little sensitive to hydrolysis as possible, ie which has the smallest possible specific surface area.
  • the LiPF 6 should be free-flowing so that it can be processed in automated systems. Finally, it should be ensured that the not inconsiderable heat of solution is released in a controlled manner in the production of electrolyte solutions.
  • Lithium hexafluorophosphate is usually prepared from purified PF 5 and lithium fluoride in a solvent (HF or organic solvents such as diethyl ether or acetonitrile). Since the PF S gas is contaminated on the one hand with impurities from the synthesis (for example POF 3 , HC1 and others) and on the other hand during the reaction with LiF in a liquid medium with traces of moisture with the release of HF, POF 3 , Li [P0 2 F 2 ] among other products, the raw product obtained generally has to be cleaned due to the high purity requirements of the battery industry.
  • a solvent HF or organic solvents such as diethyl ether or acetonitrile
  • the raw product can e.g. can be recrystallized from anhydrous HF.
  • This method has the disadvantage that the last traces of acid and lithium fluoride can only be separated off with great difficulty.
  • the corrosive and toxic properties of HF it requires complex reaction technology.
  • the process has the disadvantages that the metal hexafluorophosphates (MPF 6 ) are not available or are only available at high prices and the solutions are contaminated by the anion X (for example 0.1% KC1 or 3% KBr).
  • DE 196 32543 A describes, among other things, a process for the production of LiPF 6 from the cheap raw materials LiF and PC1 5 under autogenous pressure or optionally in organic solvents, in particular in diethyl ether, according to the equation
  • LiPF s crystallize from organic donor solvents such as diethyl ether or acetonitrile
  • the solvate complexes most of which are in the form of well-formed crystals, disintegrate into a surface-rich, poor surface when they are dried at temperatures below the solvate decomposition point manageable powder.
  • LiPF 6 is produced from LiF and PF S in ether at 0 to 50 ° C. and the LiPF 6 crystals obtained are dried at 30 to 35 ° C. under reduced pressure (0.2 mm).
  • the LiPF s isolated from ethereal solutions at temperatures of ⁇ 40 ° C contains depending on the Manufacturing conditions a certain amount of "crystal ether" (about 1 to 2 mol), which can be removed relatively quickly and completely during vacuum drying, but inevitably a dusty, surface-rich product is obtained.
  • the object of the invention is to avoid the disadvantages known from the prior art and to create a process which, starting from cheap raw materials, provides a technically simple, manageable process, an easy to handle, pure LiPF 6 , which has a purity of> 99, Has 8%.
  • a diethyl ether-containing LiF suspension is reacted with PC1 S , the LiF suspension being slightly acidified before the PC1 5 is metered in.
  • acidification for example with HCl gas, accelerates the LiPF s formation reaction and, at the same time, suppresses side reactions.
  • the phenomenon that the discoloration of the reaction mixture does not occur or is greatly delayed is also particularly striking.
  • the LiF suspension containing diethyl ether is acidified. It is also possible to acidify the diethyl ether before adding LiF and use it for slurrying the lithium fluoride.
  • Anhydrous protic acids HX are used for acidification, where X can be: a halogen, sulfate or a carboxylic acid residue.
  • Preferred acids are those whose corresponding lithium salts are as poorly soluble as possible in ether or ether / hydrocarbon mixtures.
  • HC1 and HF gas are particularly preferred, the former being particularly advantageous because of the simpler handling.
  • the acid concentration can be between 0.01 and 0.5 mmol / g suspension.
  • the range between 0.02 and 0.2 mmol / g is particularly preferred.
  • the reaction temperature is 0 to 35 ° C, the preferred range being between 15 and 30 ° C.
  • the response time will include influenced by the reaction temperature and stirring intensity. In the preferred temperature range between 15 and 30 ° C, typically 2 to 8 hours are required for a practically quantitative conversion. Depending on the reaction conditions chosen (acid concentration, metering time, stirring intensity, stoichiometry and temperatures), the reaction mixture remains colorless during the entire reaction time, or it only becomes yellowish or slightly bluish towards the end.
  • the PC1 5 is metered into the acidified, well-stirred LiF suspension at temperatures between 0 and 35 ° C.
  • the amount of PCl 5 metered in is chosen so that 6.06 to 12 mol LiF are present per mol PC1 5 . Because the theoretical
  • the reaction mixture is neutralized with a base, the amount of base to be used at least corresponds to the amount of acid used.
  • Ammonia, LiOH, Li 2 CO 3 , LiH or organolithium compounds such as methyl lithium or butyllithium can be used as bases.
  • Preferred are methyl lithium, which is available on the market in the form of an ethereal solution, and lithium hydride, which does not leave any troublesome by-products in the neutralization.
  • lithium hydride Because of the insolubility of lithium hydride, it is used (based on the amount of acid used) up to a 10-fold, preferably 3 to 6-fold, molar excess. Excess lithium hydride together with the ether-insoluble lithium halides can be conveniently removed by filtration.
  • the concentration of the lithium fluoride presented as a suspension in diethyl ether is preferably 10 to 40%.
  • Either pure, dry diethyl ether or a mixture of diethyl ether and a solvent consisting of one or more hydrocarbons is used as the reaction medium.
  • Suitable hydrocarbons are alkanes, such as, for example, preferably pentane, hexane, heptane or cyclohexane and aromatics, such as, for example, preferably toluene, xylene or ethylbenzene.
  • the amount of the additional solvent optionally used can vary within wide limits and can be, for example, 0.3 to 3 parts by weight of the amount of LiF. A further dilution is possible, but makes no sense for technical and economic reasons.
  • the solvent can either be introduced as a whole before the acidification and metering in of PC1 5 , or it can be added during the PC1 S metering or the after-reaction phase. It improves the stirrability of the reaction suspension and makes it possible to replace part of the more expensive diethyl ether. Furthermore, it can be used as a crystallization aid in the crystallization cleaning step (see below) to be carried out optionally.
  • the neutralized reaction mixture is then filtered, decanted or centrifuged to remove the insoluble by-products and the excess lithium fluoride. An ethereal LiPF 6 crude product solution is obtained in this way.
  • the raw solution is contaminated, among other things, with chlorine-containing compounds, especially PC1 3 .
  • Insoluble constituents (LiCl, LiF, LiH, LiOH) of the ethereal crude LiPF 6 product solution are filtered off, and the slightly yellowish or colorless LiPF 6 solution is either dried by evaporation or further purified by crystallization in the manner described below.
  • the diethyl ether and the solvent which may be present are distilled off at normal or only moderately reduced pressure (600 to 1000 mbar). After removal of the majority of ether, the bottom temperature is increased to 40 to 100 ° C., preferably 50 to 75 ° C., by external heating. The pressure can be removed simultaneously to remove the last diethyl ether or further solvent residues
  • Crystallization process can be selected.
  • an aprotic crystallization aid is added to the ethereal crude product solution, which does not or only very poorly dissolves LiPF s in pure form and has a higher boiling point than diethyl ether.
  • the crude product solution which has been pre-evaporated to a LiPF 6 concentration of 20 to 50%, preferably 30 to 45%, can be mixed with the crystallization aid in pure diethyl ether and then filtered.
  • This crystallization aid is e.g. another ether (methyl tert-butyl ether (MTBE), dibutyl ether, diisopropyl ether), an alkane (e.g. heptane, methylcyclohexane, octane) or an aromatic hydrocarbon (e.g. benzene, toluene, ethylbenzene) or a mixture of the substances mentioned. Heptane, methylcyclohexane, toluene and methyl tert are particularly preferred. Butyl ether.
  • MTBE methyl tert-butyl ether
  • dibutyl ether diisopropyl ether
  • an alkane e.g. heptane, methylcyclohexane, octane
  • aromatic hydrocarbon e.g. benzene, toluene, ethylbenzene
  • the amount of the crystallization aid is 0.2 to 5 parts by weight of the amount of LiPF 6 present in diethyl ether solution. 0.3 to 1.5 parts by weight, based on the dissolved LiPF ⁇ , are particularly preferred. 11
  • the LiPF 6 solution in the solvent mixture defined above is concentrated at normal or slightly reduced pressure.
  • the jacket temperature of the still is initially 40 to 70 ° C.
  • practically pure diethyl ether initially distills, which continuously worsens the solvent capacity of the remaining solvent for the impurities and also LiPF 6 .
  • Et 2 0: LiPF 6 ratio of approximately 1.2 to 2.3 is reached, the distillation is interrupted and the distillation residue is freed of any precipitated impurities by filtration.
  • the clear filtrate is then evaporated further down to a residual amount of ether of 0 to 30%.
  • the bottom temperature rises to about 40 to 90 ° C.
  • Lithium hexafluorophosphate separates out as a colorless, coarsely crystalline solid.
  • the solid is freed from the mother liquor by filtration or centrifugation. This solid / liquid is preferably
  • the crystals are washed with an aliphatic and / or aromatic hydrocarbon, preferably pentane, hexane or toluene, and then dried. Drying is preferably carried out at elevated temperatures (30 to 50 ° C.) under reduced pressure.
  • an aliphatic and / or aromatic hydrocarbon preferably pentane, hexane or toluene
  • Example 1 (Comparative example): reaction of LiF with PC1 S in neutral diethyl ether at 25 ° C. (according to German patent application 196 32543)
  • Examples 1 and 2 show that much less undesirable PC1 3 is formed by acidification and product discoloration can be largely avoided.
  • Examples 3 and 4 show that the different discoloration behavior is dependent on the acid concentration. At an acid concentration of 0.14 mmol / g, a colorless product solution was obtained even at relatively high reaction temperatures.
  • Example 5 (comparative example): total evaporation to powder
  • Examples 5 and 6 demonstrate that when the bottom temperature is increased above 40 ° C., granules can be obtained, while below 40 ° C. a yellowish, dust-fine powder is obtained, and that pure LiPF 6 is produced by the process according to the invention.
  • Example 8 Crystallization from Et 2 0 / toluene at 50 to 70 ° C
  • Examples 7 and 8 according to the invention demonstrate the different crystallization behavior of LiPF s from diethyl ether / hydrocarbon mixtures below and above about 40 ° C.
  • Example 10 Crystallization from Et 2 0 / toluene at approx. 60 ° C without polishing filtration
  • saturated hydrocarbons can be used instead of the aromatic toluene.

Abstract

L'invention concerne un procédé de production de LiPF6 pur, à partir de LiF et de PCl5 dans de l'éther diéthylique. Selon ce procédé, on acidifie une suspension de LiF dans de l'éther diéthylique, avec un acide anhydre protique HX, puis on la fait réagir avec du PCl5. Ce mélange, après avoir réagi, est neutralisé, filtré et soit évaporé jusqu'à siccité totale, soit cristallisé au moyen d'un auxiliaire de cristallisation.
PCT/EP1999/000141 1998-02-12 1999-01-13 PROCEDE DE PRODUCTION DE LiPF6 PUR WO1999041193A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1998105356 DE19805356C1 (de) 1998-02-12 1998-02-12 Verfahren zur Herstellung von reinem LiPF¶6¶
DE19805356.8 1998-02-12

Publications (1)

Publication Number Publication Date
WO1999041193A1 true WO1999041193A1 (fr) 1999-08-19

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DE (1) DE19805356C1 (fr)
WO (1) WO1999041193A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10296746B4 (de) * 2002-03-21 2007-02-15 Council Of Scientific And Industrial Research Neues thermisches Festkörperverfahren zur Synthese von Lithiumhexafluorphosphat
EP1873861A1 (fr) * 2005-04-19 2008-01-02 Central Glass Company, Limited Procede de production d'une solution electrolytique pour une batterie a ions lithium et batterie l'utilisant

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5862094B2 (ja) 2010-08-17 2016-02-16 セントラル硝子株式会社 ヘキサフルオロリン酸リチウム濃縮液の製造方法
CN102275895B (zh) * 2011-06-30 2013-07-31 湖北省宏源药业有限公司 一种合成六氟磷酸锂的方法
EP2607305A1 (fr) 2011-12-23 2013-06-26 LANXESS Deutschland GmbH Solutions de LiPF6
EP2607316A1 (fr) 2011-12-23 2013-06-26 LANXESS Deutschland GmbH Solutions LiPF6
EP2607315A1 (fr) 2011-12-23 2013-06-26 LANXESS Deutschland GmbH Solutions LiPF6
EP2607306A1 (fr) 2011-12-23 2013-06-26 LANXESS Deutschland GmbH Solutions de lipf6

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3594402A (en) * 1969-05-29 1971-07-20 United States Steel Corp Tetraacetonitrilolithiumhexafluorophosphate and method for the preparation thereof
US3607020A (en) * 1970-03-19 1971-09-21 Foote Mineral Co Preparation of lithium hexafluorophosphate
CA2193119A1 (fr) * 1995-12-14 1997-06-15 Shouichi Tsujioka Solution electrolytique pour piles au lithium et procede de production
DE19625448A1 (de) * 1996-06-26 1998-01-02 Solvay Fluor & Derivate Verfahren zur Herstellung von LiPF¶6¶

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5378445A (en) * 1993-12-23 1995-01-03 Fmc Corporation Preparation of lithium hexafluorophosphate solutions
DE19632543C1 (de) * 1996-08-13 1998-04-02 Metallgesellschaft Ag Verfahren zur Herstellung von LiPF¶6¶

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3594402A (en) * 1969-05-29 1971-07-20 United States Steel Corp Tetraacetonitrilolithiumhexafluorophosphate and method for the preparation thereof
US3607020A (en) * 1970-03-19 1971-09-21 Foote Mineral Co Preparation of lithium hexafluorophosphate
FR2084920A5 (fr) * 1970-03-19 1971-12-17 Foote Mineral Co
CA2193119A1 (fr) * 1995-12-14 1997-06-15 Shouichi Tsujioka Solution electrolytique pour piles au lithium et procede de production
DE19625448A1 (de) * 1996-06-26 1998-01-02 Solvay Fluor & Derivate Verfahren zur Herstellung von LiPF¶6¶

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10296746B4 (de) * 2002-03-21 2007-02-15 Council Of Scientific And Industrial Research Neues thermisches Festkörperverfahren zur Synthese von Lithiumhexafluorphosphat
EP1873861A1 (fr) * 2005-04-19 2008-01-02 Central Glass Company, Limited Procede de production d'une solution electrolytique pour une batterie a ions lithium et batterie l'utilisant
EP1873861A4 (fr) * 2005-04-19 2011-10-19 Central Glass Co Ltd Procede de production d'une solution electrolytique pour une batterie a ions lithium et batterie l'utilisant
US8097360B2 (en) 2005-04-19 2012-01-17 Central Glass Company, Limited Method for producing electrolyte solution for lithium ion battery and battery using same

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Publication number Publication date
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