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Preparation of Lithium Hexafluorophosphate Solutions Herstellung Von Lithiumhexafluorphosphatlosungen Preparation De Solutions D'hexafluorophosphate De Lithium

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Preparation of Lithium Hexafluorophosphate Solutions Herstellung Von Lithiumhexafluorphosphatlosungen Preparation De Solutions D'hexafluorophosphate De Lithium _ <v Europaisches llll II || IMI 1 1 1 1| UN || I I JGV/l Eur°Pean Patent Office <*S Office europeen des brevets (11) EP 0 735 983 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) int. CI.6: C01 B 25/10, H01M6/14, of the grant of the patent: C01 D 1 5/00, H01 M 6/1 6, 31.03.1999 Buiietin 1999/13 H01M 10/40 (21) Application number: 94926652.2 (86) International application number: (22) Date of filing: 02.09.1994 PCT/US94/09843 (87) International publication number: WO 95/17346 (29.06.1995 Gazette 1995/27) (54) PREPARATION OF LITHIUM HEXAFLUOROPHOSPHATE SOLUTIONS HERSTELLUNG VON LITHIUMHEXAFLUORPHOSPHATLOSUNGEN PREPARATION DE SOLUTIONS D'HEXAFLUOROPHOSPHATE DE LITHIUM (84) Designated Contracting States: • BARNETT, Rebecca, A. DE FR Maiden, NC 28650 (US) (30) Priority: 23.12.1993 US 172690 (74) Representative: McCall, John Douglas et al (43) Date of publication of application: WP. THOMPSON & CO. 09.10.1996 Bulletin 1996/41 Coopers Building Church Street (73) Proprietor: FMC CORPORATION Liverpool L1 3AB (GB) Philadelphia, PA 19103 (US) (56) References cited: (72) Inventors: EP-A- 0 643 433 US-A- 3 654 330 • SALMON, Dennis, J. US-A-4 880 714 Gastonia, NC 28054 (US) • BARNETTE, D. Wayne • PATENT ABSTRACTS OF JAPAN vol. 008, no. Bessemer City, NC 28016 (US) 142 (E-254), 3 July 1984 & JP-A-59 051475 (SANYO DENKI KK), 24 March 1984, CO CO CO <7> IO CO Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in o a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. Q_ 99(1) European Patent Convention). LU Printed by Xerox (UK) Business Services 2.16.7/3.6 1 EP 0 735 983 B1 2 Description cation difficult. One preparation method reacts lithium hydride (LiH) and phosphorus pentachloride (PCI5) in [0001] This invention concerns a manufacturing the presence of hydrofluoric acid anhydride. The proc- method for high purity, battery quality, lithium hexaf luor- ess starts with solid PCI5 which always contains some ophosphate and high purity, lithium hexafluorophos- s moisture, sulfate ions, iron and lead which impurities phate solutions suitable for use in high energy batteries. contaminate the electrolyte; unfortunately even rela- [0002] The high voltages of primary lithium batteries tively small amounts of these impurities are unaccepta- and the charging voltage for secondary lithium battery ble in electrolytes. Another method reacts a lithium designs place a demanding requirement on the electro- halide and PF6 in hydrofluoric acid anhydride, this proc- lyte salt chosen for these battery applications. The salt 10 ess, employing the solid gas reaction of porous LiF-HF must have sufficient electrochemical stability to avoid with PF6 gas, avoids the moisture problems of earlier reduction reactions, sufficient chemical stability to avoid processes; however high purity PF5 gas is extremely reaction with the other battery components and suffi- expensive. The process of published Japanese pub- cient solubility in the electrolyte solvent (or polymeric lished application Hei 4-175216 (1992) claims to over- matrix) to allow sufficient conductivity for the discharge 15 come the high PF5 costs by reacting PCI5 and of primary batteries and for the charging of secondary hydrofluoric acid at -20 °C or lower and an HF solution, batteries. HPF6, is formed. This resultant reaction solution is [0003] Lithium hexafluorophosphate meets the elec- warmed up to -10 °C to 20 °C to produce high purity PF5 trochemical and conductivity requirements for many gas. The PF5 gas is introduced carefully into a solution battery applications. However, the salt is chemically 20 of LiF-HF to produce LiPF6 at -30 °C. The LiPF6 precip- very reactive and difficult to manufacture and purify. The itates as 2-3 mm particles which are recovered using use of this salt as the electrolyte salt in a lithium battery usual methods of recovery. A process is known in which can lead to reactions with other battery components NH4PF6 is reacted with LiBr in dimethoxyethane (DME) and thermal decomposition of the salt. Lithium hex- to form a LiPF6 • DME complex. The product has high afluorophosphate prepared from aqueous solutions of 25 purity but the DME is very difficult to remove which limits hexaf luorophosphoric acid and a basic lithium salt, such the product to uses where the DME can be tolerated. as lithium hydroxide or lithium carbonate, can hydrolyze [0006] Processing to avoid contamination by acidic to form three anions P02F2-, HPO3F", and P04. Thus, components has been described. US Patent 4,880,714 the precipitated lithium hexafluorophosphate salt pre- discloses the reaction of a salt with a cation containing pared from aqueous solutions will contain these unde- 30 an adduct of a proton and a Lewis base and an anion sirable contaminants. These hydrolysis reactions will consisting of hexafluorophosphate in an ether with a yield acids which catalyzes the hydrolysis reaction. The lithium base to form a solution from which the LiPF6- poor thermal stability of lithium hexafluorophosphate ether complex can be isolated. Due to difficulties in makes removal of water, in order to produce anhydrous removing the ether from the complex, the complex must lithium hexafluorophosphate, extremely difficult. Conse- 35 be incorporated directly into the battery electrolyte and, quently lithium hexafluorophosphate prepared by aque- thus, this product is not useful for battery designs not ous routes are generally unsuitable for battery containing the ether. applications. The potential exists for acid catalyzed [0007] The reaction of potassium hexafluorophos- decomposition reactions with other solvents. phate with lithium bromide in acetonitrile is described to [0004] To avoid the problems of dealing with hydroly- 40 yield a potassium bromide precipitate, which is filtered, sis of the hexafluorophosphate anion in aqueous solu- and a solution of lithium hexafluorophosphate in ace- tions, processes were developed whereby lithium tonitrile recovered. Removal of acetonitrile, extraction hexafluorophosphate was produced by reactions of sus- by a halogenated hydrocarbon solvent, and filtration of pended lithium fluoride and gaseous phosphorous pen- impurities yields a solution from which crystalline tafluoride in organic solvents. The difficulties of these 45 [Li(CH3CN)4 PF6] can be isolated by removal of the processing methods include handling extremely reac- organic solvent. This product is limited to battery appli- tive, expensive phosphorous pentaf luoride gas and diffi- cations containing acetonitrile as an electrolyte compo- cult isolation of the non-solvated salt from the organic nent and is not generally suitable for batteries. solution. The reaction of lithium halides with phospho- [0008] The present invention provides a process rous pentafluoride in anhydrous hydrofluoric acid sol- so which overcomes the problems for producing battery vent has been described. Descriptions of further quality lithium hexafluorophosphate solutions by react- processing to reduce cost and increase purity are ing, under basic conditions, lithium salts with alkali revealed. These procedures leave a residual hydrofluo- metal or ammonium or organoammonium salts of hex- ric acid contained in the solid product which cannot be af luorophosphoric acid in a non-protic organic solvent in completely removed and may be detrimental to battery 55 a reaction zone that is continuously saturated with a performance. compound selected from anhydrous ammonia, methyl [0005] Lithium hexafluorophosphate is extremely amine or ethyl amine. In particular embodiments of this hygroscopic which has made its manufacture and purifi- invention, ammonia or other volatile amines are added 2 3 EP 0 735 983 B1 4 to increase the rate of the reaction as well as to precipi- more to complete. Ammonia is added at a rate to pro- tate acidic contaminants from the reactant hexafluoro- vide continuous saturation of the atmosphere in the phosphate salt. A variety of organic solvents can be reaction zone with ammonia. The reaction zone may be used in the processing, and in preferred embodiments constructed of any convent material inert to the reac- low boiling organic solvents are used so that the initial 5 tants and products. solvent can be removed in the presence of another [0013] The reactants, LiCI and KPF6 are employed in higher boiling solvent to prepare the final battery elec- substantially stoichiometric amounts with a slight trolyte solutions. The advantages of this process excess of LiCI generally being employed. Anhydrous include avoidance of acidic conditions which can yield ammonia is used in substantial amounts as it is desira- undesired decomposition reactions and avoidance of w ble to keep the reaction solution saturated with ammo- the thermally unstable solid salt; for example, by satu- nia. Stopping the ammonia addition apparently stops rating the reaction solution with anhydrous ammonia. the reaction. The reaction is ordinarily done under ambi- The reaction is optionally, beneficially conducted in the ent pressure and temperature conditions. Reaction presence of an amine which can be easily removed under pressure can be done; the reaction is best con- when the reaction is completed; for example by use of 75 ducted in an ammonia saturated atmosphere. Addition methyl or ethyl amine. of the ammonia causes a small exotherm, otherwise the [0009] A variety of reactant lithium salts useful in prac- reaction is done under ambient temperature and pres- ticing this invention include but are not limited to lithium sure conditions. Ammonia advantageously is added chloride, lithium bromide, lithium perchlorate, lithium throughout the reaction period. tetrafluoroborate, lithium nitrate, lithium acetate, lithium 20 [0014] Battery quality electrolytes based on LiPF6 dis- benzoate and the like. Choice is usually governed by solved in organic solvents are useful battery electro- solubility of the by-product salt formed from the cation of lytes.
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