EP2984038A2 - Électrolyte pauvre en chlorure - Google Patents

Électrolyte pauvre en chlorure

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Publication number
EP2984038A2
EP2984038A2 EP14716348.9A EP14716348A EP2984038A2 EP 2984038 A2 EP2984038 A2 EP 2984038A2 EP 14716348 A EP14716348 A EP 14716348A EP 2984038 A2 EP2984038 A2 EP 2984038A2
Authority
EP
European Patent Office
Prior art keywords
organic solvent
lithium
ppm
hydrogen chloride
lithium hexafluorophosphate
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.)
Withdrawn
Application number
EP14716348.9A
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German (de)
English (en)
Inventor
Thomas Linder
Matthias Boll
Eberhard Kuckert
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lanxess Deutschland GmbH
Original Assignee
Lanxess Deutschland GmbH
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 Lanxess Deutschland GmbH filed Critical Lanxess Deutschland GmbH
Priority to EP14716348.9A priority Critical patent/EP2984038A2/fr
Publication of EP2984038A2 publication Critical patent/EP2984038A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a process for the preparation of low-lithium lithium hexafluorophosphate starting from lithium fluoride and phosphorus pentafluond and its use in an electrolyte.
  • Lithium hexafluorophosphate (LiPF 6 ) has attained great industrial importance, especially as conducting salt in the production of powerful batteries. In order to ensure the functionality and service life and thus the quality of such accumulators, it is of particular importance that the lithium compounds used contain as low as possible amounts of chloride. Chloride ions are blamed for cell shorts due to corrosion.
  • DE19712988A1 describes a batchwise process starting from phosphorus trichloride (PCI 3 ).
  • PCI 3 phosphorus trichloride
  • phosphorus trichloride was submitted, then added hydrogen fluoride and then elemental chlorine.
  • the resulting gaseous mixture of hydrogen chloride and phosphorus pentafluoride was passed over the lithium fluoride in the experimental reactor to obtain lithium hexafluorophosphate.
  • JP1 1 171518A2 describes a process for the preparation of lithium hexafluorophosphate which proceeds from phosphorus trichloride and hydrogen fluoride via phosphorus trifluoride, the latter being reacted with elemental chlorine first to phosphorodichloride trifluoride, this in turn with hydrogen fluoride to phosphorus pentafluoride and the latter finally with lithium fluoride to lithium hexafluorophosphate in an organic solvent.
  • the organic solvents used are diethyl ether and dimethyl carbonate.
  • No. 3,594,402 describes the preparation of improved lithium hexafluorophosphate from tetraacetonitrile lithium hexafluorophosphate by reaction of lithium fluoride and phosphorus pentafluoride with excess acetonitrile. The removal of the excess acetonitrile is carried out under vacuum.
  • US5378445 discloses a process for preparing solutions of lithium hexafluorophosphate comprising reacting a lithium salt, under basic conditions, with a salt consisting of sodium, potassium, ammonium or an organo-ammonium hexafluorophosphate salt in a low-boiling one -protonic organic solvent.
  • a solution containing lithium hexafluorophosphate and a precipitated sodium, potassium, ammonium or organoammonium salt containing the anion of the lithium salt reactant is thereby obtained.
  • lithium hexafluorophosphate a production method for lithium hexafluorophosphate is described.
  • phosphorus pentafluoride is prepared from calcium fluoride and phosphorus pentoxide.
  • Lithium hexafluorophosphate was synthesized in an acetonitrile solution by the reaction of lithium fluoride with Phosphorus pentafluond at room temperature. The purity of the produced lithium hexafluorophosphate was 99.98%.
  • the object of and the subject of the present invention is now a process for preparing low-lithium lithium hexafluorophosphate comprising at least the steps of a) contacting lithium fluoride in a first organic solvent containing a nitrile with a gas containing phosphorus pentafluoride and hydrogen chloride, wherein a reaction mixture comprising lithium hexafluorophosphate, a first organic solvent containing a nitrile and hydrogen chloride is obtained, b) contacting the reaction mixture formed according to a) with further organic solvent which is different from the first organic solvent, lithium hexafluorophosphate precipitating and c) separating off precipitated lithium hexafluorophosphate,
  • step a) lithium fluoride in a first organic solvent is contacted with a gas containing phosphorus pentafluond and hydrogen chloride to obtain a reaction mixture containing lithium hexafluorophosphate, a first organic solvent and hydrogen chloride.
  • the lithium fluoride used in step a) has, for example, a purity of 98.0000 to 99.9999% by weight, preferably 99.0000 to 99.9999% by weight, more preferably 99.9000 to 99.9995% by weight. , more preferably 99.9500 to 99.9995 Wt .-% and most preferably 99.9700 to 99.9995 wt .-% based on anhydrous product.
  • the lithium fluoride used furthermore preferably has foreign ions:
  • the lithium fluoride used further has, for example, at foreign ions i) a content of 0.1 to 1000 ppm, preferably from 0.1 to 100 ppm and more preferably 0.5 to 10 ppm of sulfate and / or ii) a content of 0.1 to 1000 ppm, preferably 0.5 to 500 ppm chloride, also based on the anhydrous product and it is true that the sum of lithium fluoride and the aforementioned foreign ions does not exceed 1, 000,000 ppm, based on the total weight of the technical lithium carbonate based on the anhydrous product.
  • the lithium fluoride contains a total of foreign metal ion content of 1000 ppm or less, preferably 300 ppm or less, more preferably 20 ppm or less, and most preferably 10 ppm or less.
  • the lithium fluoride with the aforementioned specifications can be obtained, for example, by a process comprising at least the following steps: i) providing an aqueous medium containing dissolved lithium carbonate ii) reacting the aqueous medium provided according to a) with gaseous hydrogen fluoride to form an aqueous suspension of solid lithium fluoride iii) Separation of the solid lithium fluoride from the aqueous suspension. Iv) Drying of the separated lithium fluoride.
  • step i) an aqueous solution containing lithium carbonate is provided.
  • aqueous medium containing dissolved lithium carbonate is to be understood here as meaning a liquid medium which contains i) dissolved lithium carbonate, preferably in an amount of at least 2.0 g / l, more preferably 5.0 g / l to maximum solubility in the aqueous medium at the selected temperature, most preferably 7.0 g / l to the maximum solubility in the aqueous medium at the selected temperature, in particular the content of lithium carbonate is 7.2 to 15.4 g / l in that the solubility of lithium carbonate in pure water at 0 ° C is 15.4 g / l at 20 ° C 13.3 g / l, at 60 ° C 10.1 g / l and at 100 ° C 7.2 g / l l) and consequently certain concentrations can only be achieved at certain temperatures ii) contains at least 50% by weight of water, preferably 80% by weight, more preferably at least 90% by weight, based on the total weight of the liquid medium,
  • the aqueous medium containing dissolved lithium carbonate may contain, as further component iv), at least one water-miscible organic solvent.
  • Suitable water-miscible organic solvents are, for example, monohydric or polyhydric alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, ethylene glycol, ethylene glycol monomethyl ether,
  • Ethylene glycol monoethyl ether propylene glycol, 1,3-propanediol or glycerol, ketones such as acetone or ethyl methyl ketone.
  • the aqueous medium containing dissolved lithium carbonate contains at least one water-miscible organic solvent
  • their proportion may be, for example, more than 0.0% by weight to 20% by weight, preferably 2 to 10% by weight, in which case in each case in that the sum of the components i), ii), iii) and iv) contains a maximum of 100% by weight, preferably 95 to 100% by weight and particularly preferably 98 to 100% by weight, based on the total weight of the aqueous medium dissolved lithium carbonate is.
  • the aqueous medium containing dissolved lithium carbonate is free of water-miscible organic solvents.
  • the aqueous medium containing dissolved lithium carbonate may contain as further component v) a complexing agent, preferably in an amount of 0.001 to 1 wt .-%, preferably 0.005 to 0.2% by weight based on the total weight of the aqueous medium containing dissolved lithium carbonate.
  • Complexing agents are preferably those whose complexes with calcium ions and magnesium ions form complexes which have a solubility of more than 0.02 mol / l at a pH of 8 and 20 ° C.
  • the aqueous medium containing dissolved lithium carbonate is free of complexing agents.
  • the procedure is preferably such that solid lithium carbonate is brought into contact with a lithium carbonate-free or lithium-carbonate-poor aqueous medium so that the solid lithium carbonate at least partially dissolves.
  • a low-lithium carbonate aqueous medium is understood as meaning an aqueous medium which has a lithium carbonate content of up to 1.0 g / l, preferably up to 0.5 g / l, of lithium carbonate but is not free of lithium carbonate.
  • the aqueous medium used for the preparation fulfills the conditions mentioned above under ii) and iii) and optionally comprises the components iv) and v).
  • the aqueous medium is water, preferably water having a specific electric resistance of 5 MQ "cm at 25 ° C or more.
  • steps i) to iv) are repeated one or more times, repeated one or more times.
  • the aqueous medium obtained in a previous step iii) in the separation of solid lithium fluoride from the aqueous suspension of lithium fluoride in the repetition for providing the aqueous medium containing dissolved lithium carbonate used as lithium carbonate-free or lithium carbonate poor aqueous medium, the aqueous medium obtained in a previous step iii) in the separation of solid lithium fluoride from the aqueous suspension of lithium fluoride.
  • the lithium carbonate-free or lithium carbonate-poor aqueous medium contains dissolved lithium fluoride, typically up to the saturation limit at the respective temperature.
  • contacting the lithium carbonate-free or aqueous medium with the solid lithium carbonate may be accomplished in a stirred reactor, flow-through reactor, or other apparatus known to those skilled in the art for contacting liquid with solids.
  • a stirred reactor flow-through reactor, or other apparatus known to those skilled in the art for contacting liquid with solids.
  • an excess of lithium carbonate is used, i. so much that complete dissolution of the solid lithium carbonate can not occur.
  • filtration, sedimentation, centrifugation or any other method known to the person skilled in the art for the separation of solids from or from liquid is then carried out, filtration being preferred.
  • the temperature during contacting can be carried out, for example, from the freezing point to the boiling point of the aqueous medium used, preferably 0 to 100.degree. C., particularly preferably 10 to 60.degree. C. and particularly preferably 10 to 35.degree. C., in particular 16 to 24.degree.
  • the pressure when contacting can be, for example, 100 hPa to 2 MPa, 900 hPa to 1200 hPa, in particular ambient pressure is particularly preferred.
  • lithium carbonate which has a purity of 95.0 to 99.9% by weight, preferably 98.0 to 99.8% by weight and particularly preferably 98.5 to 99.8% by weight. -% based on anhydrous product possesses.
  • the technical lithium carbonate further contains foreign ions, i. ions that are not lithium or carbonate ions
  • the sum of lithium carbonate and the abovementioned foreign ions 1) to 4) and optionally i) and ii) does not exceed 1, 000,000 ppm, based on the total weight of the technical lithium carbonate, based on the anhydrous product.
  • the technical lithium carbonate has a purity of 98.5 to 99.5 wt .-% and a content of 500 to 2000 ppm of foreign metal ions ie sodium, potassium, magnesium and calcium.
  • the technical lithium carbonate preferably additionally has a content of 100 to 800 ppm of foreign anions, i. Sulphate or chloride based on the anhydrous product.
  • the aqueous medium containing dissolved lithium carbonate prepared according to step i) typically has a pH of 8.5 to 12.0, preferably of 9.0 to 11.5, measured or calculated at 20 ° C. and 1013 hPa.
  • the aqueous medium containing dissolved lithium carbonate provided in step i) Before the aqueous medium containing dissolved lithium carbonate provided in step i) is used in step (ii), it can be passed through an ion exchanger, in order to at least partially remove calcium and magnesium ions in particular.
  • an ion exchanger for example, weakly or strongly acidic cation exchangers can be used for this purpose.
  • the ion exchangers can be used in devices, such as, for example, flow columns which are filled with the cation exchangers described above, for example in the form of powders, beads or granules.
  • ion exchangers containing copolymers of at least styrene and divinylbenzene which also contain, for example, aminoalkylenephosphonic acid groups or iminodiacetic acid groups.
  • Such ion exchangers are, for example, those of the Lewatit TM type such as Lewatit TM OC 1060 (AMP type), Lewatit TM TP 208 (IDA type), Lewatit TM E 304/88, Lewatit TM S 108, Lewatit TP 207, Lewatit TM S 100; those of the type Amberlite TM such as Amberlite TM IR 120, Amberlite TM IRA 743; those of the Dowex TM type, such as Dowex TM HCR; those of the Duolite type, such as Duolite TM C 20, Duolite TM C 467, Duolite TM FS 346; and Imac TM type such as Imac TM TMR, with Lewatit TM types being preferred.
  • Lewatit TM type such as Lewatit TM OC 1060 (AMP type), Lewatit TM TP 208 (IDA type), Lewatit TM E 304/88, Lewatit
  • such ion exchangers are used, which are as low-sodium as possible.
  • no treatment with ion exchangers takes place.
  • step ii) the reaction of the aqueous medium provided according to step i) comprising dissolved lithium carbonate with gaseous hydrogen fluoride is carried out to give an aqueous suspension of solid lithium fluoride.
  • the reaction can be carried out, for example, by introducing or passing a gaseous hydrogen fluoride-containing gas stream into or over the aqueous medium containing dissolved lithium carbonate, or by spraying, atomizing or flowing through the aqueous medium containing dissolved lithium carbonate in or through a gas containing gaseous hydrogen fluoride.
  • Gaseous hydrogen fluoride contained as a gaseous hydrogen fluoride gas or gas containing gaseous hydrogen fluoride can be used as such or a gas containing gaseous hydrogen fluoride and an inert gas, an inert gas is to be understood as a gas that does not react with lithium fluoride under the usual reaction conditions.
  • gases are air, nitrogen, argon and other noble gases or carbon dioxide, with air and more nitrogen being preferred.
  • the proportion of inert gas can vary as desired and, for example, 0.01 to 99 vol .-%, preferably 1 to 20 vol .-%.
  • lithium fluoride is formed, which precipitates due to the fact that it is less soluble in the aqueous medium than lithium carbonate, and consequently forms an aqueous suspension of solid lithium fluoride. It is known to those skilled in the art that lithium fluoride has a solubility of about 2.7 g / l at 20 ° C.
  • the reaction is preferably carried out in such a way that the resulting aqueous suspension of solid lithium fluoride reaches a pH of 3.5 to 8.0, preferably 4.0 to 7.5, and more preferably 5.0 to 7.2. Carbon dioxide is liberated at the stated pH values.
  • the temperature in the reaction according to step ii) can be, for example, from the freezing point to the boiling point of the aqueous medium containing dissolved lithium carbonate, preferably 0 to 65 ° C, more preferably 15 to 45 ° C and particularly preferably 15 to 35 ° C, especially 16 up to 24 ° C.
  • the pressure in the reaction according to step ii) can be, for example, 100 hPa to 2 MPa, 900 hPa to 1200 hPa, in particular ambient pressure is particularly preferred.
  • step iii) the separation of the solid lithium fluoride from the aqueous suspension. Separation is accomplished, for example, by filtration, sedimentation, centrifugation, or any other method known to those skilled in the art for separating solids from or from liquids, with filtration being preferred.
  • the solid lithium fluoride thus obtained typically still has a residual moisture of from 1 to 40% by weight, preferably from 5 to 30% by weight.
  • step iii) Before the lithium fluoride separated in step iii) is dried according to step iv), it can be washed once or several times with water or a medium containing water and water-miscible organic solvents. Water is preferred. Water having an electric resistance of 15 MQ "cm at 25 ° C or more particularly preferred. From step iii) adhering to the solid lithium fluoride water with foreign ions is thereby removed as far as possible.
  • the lithium fluoride is dried.
  • the drying can be carried out in any apparatus known to the person skilled in the art for drying.
  • the drying is carried out by heating the lithium fluoride, preferably at 100 to 800 ° C, more preferably 200 to 500 ° C.
  • the first organic solvent for example, a nitrile, a combination of nitriles or a combination of at least one nitrile with at least one non-nitrile organic solvent may be used.
  • Suitable nitriles are acetonitrile, propanenitrile and benzonitrile. Particular preference is given to using acetonitrile.
  • the molar ratio of nitriles used to the amount of lithium ions present in the reaction mixture from step a) is at least 1: 1, preferably at least 10: 1 and more preferably at least 50: 1 and most preferably at least 100: 1.
  • the first organic solvent When used as the first organic solvent are those which are not nitrile, those organic solvents are preferably used which are liquid at room temperature and have a boiling point of 300 ° C or less at 1013 hPa and further at least one oxygen atom or a nitrogen atom or both contain.
  • Preferred organic solvents are those which have no protons which have a pKa value at 25 ° C., based on water or an aqueous comparison system of less than 20. Such organic solvents are also referred to in the literature as "aprotic" solvents.
  • Examples of such other organic solvents are liquid at room temperature esters, organic carbonates, ketones, ethers, acid amides or sulfones.
  • Examples of ethers are diethyl ether, diisopropyl ether, methyl tert-butyl ether, ethylene glycol dimethyl and diethyl ether, 1, 3-Propandioldimethyl and diethyl ether, dioxane and tetrahydrofuran.
  • esters are methyl and ethyl acetate and butyl acetate or organic carbonates such as dimethyl carbonate (DMC), diethyl carbonate (DEC) or propylene carbonate (PC) or ethylene carbonate (EC).
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • PC propylene carbonate
  • EC ethylene carbonate
  • An example of a sulphone is sulfolane.
  • ketones are acetone, methyl ethyl ketone and acetophenone.
  • acid amides are N, N-dimethylformamide, ⁇ , ⁇ -dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide.
  • the first organic solvent according to the invention may also contain several of said organic solvents.
  • solid lithium fluoride is contacted with a first organic solvent.
  • a first organic solvent is initially charged and solid lithium fluoride is added.
  • the resulting suspension containing lithium fluoride and a first organic solvent is contacted with gas containing phosphorus pentafluoride and hydrogen chloride.
  • the contacting of lithium fluoride and a first organic solvent takes place under inert gas, preferably under argon.
  • step a) comprising phosphorus pentafluoride and hydrogen chloride can be prepared in a manner known per se by a process comprising at least the following steps.
  • the gas containing phosphorus pentafluoride and hydrogen chloride there is typically used a gas mixture containing 5 to 41% by weight of phosphorus pentafluoride and 6 to 59% by weight of hydrogen chloride, preferably 20 to 41% by weight of phosphorus pentafluond and 40 to 59% by weight of hydrogen chloride preferably 33 to 41 wt .-% phosphorus pentafluond and 49 to 59 wt .-% hydrogen chloride are used, wherein the proportion of phosphorus pentafluoride and hydrogen chloride, for example, 1 1 to 100 wt .-%, preferably 90 to 100 wt .-% and particularly preferably 95 to 100 wt .-% is.
  • the difference to 100 wt .-%, if present at all, may be chlorine, hydrogen fluoride or inert gases, wherein an inert gas is to be understood here as a gas which does not react with phosphorus pentafluoride, fluorine or hydrogen chloride or lithium fluoride under the usual reaction conditions.
  • an inert gas is to be understood here as a gas which does not react with phosphorus pentafluoride, fluorine or hydrogen chloride or lithium fluoride under the usual reaction conditions.
  • nitrogen, argon and other noble gases or carbon dioxide with nitrogen being preferred.
  • the difference to 100 wt .-%, if any, may alternatively or additionally continue to be hydrogen fluoride.
  • hydrogen fluoride is used, for example, in an amount of 4.5 to 8 mol, preferably 4.8 to 7.5 mol and more preferably 4.8 to 6.0 mol of hydrogen fluoride per mole of phosphorus trichloride used.
  • the gas containing phosphorus pentafluond and hydrogen chloride is therefore typically a gas mixture containing 5 to 41% by weight of phosphorus pentafluond, 6 to 59% by weight of hydrogen chloride and 0 to 50% by weight of hydrogen fluoride, preferably 20 to 41% by weight of phosphorus pentafluond, 40 to 59 wt .-% of hydrogen chloride and 0 to 40 wt .-% of hydrogen fluoride, particularly preferably 33 to 41 wt .-% phosphorus pentafluond, 49 to 59 wt .-% hydrogen chloride and 0 to 18 wt .-% hydrogen fluoride, wherein the proportion of Phosphorus pentafluoride, hydrogen chloride and hydrogen fluoride, for example, 1 1 to 100 wt .-%, preferably 90 to 100 wt .-% and particularly preferably 95 to 100 wt .-% is.
  • gas comprising phosphorus pentafluoride and hydrogen chloride in step a) is understood to mean that the suspension containing lithium fluoride and a first organic solvent is contacted first with hydrogen chloride gas and then with phosphorus pentafluoride gas.
  • gas comprising phosphorus pentafluoride and hydrogen chloride in step a) is understood to mean that the suspension containing lithium fluoride and first organic solvent is first brought into contact with phosphorus pentafluoride gas and subsequently with hydrogen chloride gas.
  • the reaction pressure in step a) is, for example, 500 hPa to 5 MPa, preferably 900 hPa to 1 MPa, and more preferably 0, 1 MPa to 0.5 MPa.
  • the reaction temperature in step a) is for example -60 ° C to 150 ° C, preferably between 20 to 150 ° C and most preferably between -10 ° C and 20 ° C or between 50 and 120 ° C. At temperatures above 120 ° C., it is preferable to work under a pressure of at least 1500 hPa.
  • the reaction time in step a) is for example 10 seconds to 24 hours, preferably 5 minutes to 10 hours.
  • the gas leaving the reaction vessel in an aqueous solution of alkali hydroxide preferably an aqueous solution of potassium hydroxide, more preferably in a 5 to 30 wt .-%, most preferably in a 10 to 20 wt .-%, in particular preferably in a 15 wt .-% solution of potassium hydroxide in water collected.
  • the preparation of the gas or gas mixture used in step a) takes place in the gas phase.
  • the reactors to be used for this purpose preferably tube reactors, in particular stainless steel tubes, and the reaction vessels to be used for the synthesis of the lithium hexafluorophosphate are known to the person skilled in the art and are described, for example, in the Textbook of Technical Chemistry - Volume 1, Chemical Reaction Engineering, M. Baerns, H. Hofmann, A. Renken , Georg Thieme Verlag Stuttgart (1987), pp. 249-256.
  • the contacting according to step a) can be carried out, for example, by introducing the gas containing phosphorus pentafluoride and hydrogen chloride into the suspension.
  • the gas containing phosphorus pentafluoride and hydrogen chloride is passed over the suspension containing lithium fluoride and a first organic solvent.
  • the temperature during the contacting according to step a) can be carried out, for example, from the freezing point to the boiling point of the aqueous medium used, preferably 0 to 100 ° C, more preferably 10 to 60 ° C and particularly preferably 10 to 35 ° C, especially 16 to 24 ° C. ,
  • the pressure during the contacting according to step a) can be, for example, 100 hPa to 2 MPa, 900 hPa to 1200 hPa, in particular ambient pressure is particularly preferred.
  • step a) can be carried out, for example, continuously or batchwise in any reaction vessel known to the person skilled in the art for the reaction of liquids with gases, which is preferably resistant to hydrogen fluoride, such as those of Teflon.
  • the resulting reaction mixture is stirred with lithium fluoride in a first organic solvent during contacting, alternatively during and after contacting, or, alternatively, after contacting the gas containing phosphorus pentafluoride and hydrogen chloride.
  • the contacting can be facilitated by introducing mixing energy e.g. by static or non-static mixing elements.
  • the prepared reaction mixture containing lithium hexafluorophosphate, a first organic solvent and hydrogen chloride is stirred for example for a period of 10 seconds to 24 hours, preferably 5 minutes to 12 hours, more preferably 10 minutes to 4 hours and most preferably 30 minutes to 2 hours and then filtered, preferably through a filter having a pore size of 50 nm.
  • the further organic solvent according to the invention is characterized in that in the other organic solvent lithium hexafluorophosphate a lower solubility than in the first organic solvent.
  • the temperature during the contacting can take place, for example, and preferably from the freezing point to the boiling point of the organic solvent or its low-boiling component used, for example from -45 to 80.degree. C., more preferably from 10 to 60.degree. C. and particularly preferably from 10 to 35.degree , in particular from 16 to 24 ° C.
  • the pressure when contacting can be, for example, from 100 hPa to 2 MPa, preferably from 900 hPa to 1200 hPa, ambient pressure is particularly preferred.
  • Preferred as another organic solvent is toluene.
  • the solubility of lithium hexafluorophosphate in the first organic solvent and in the other organic solvent as such can be determined by a few preliminary experiments.
  • the first organic solvent according to the invention and the further organic solvent are preferably subjected to a drying process prior to their use, more preferably a drying process over a molecular sieve.
  • the content of impurities, in particular water, of the first organic solvent according to the invention and of the further organic solvent should be as low as possible. In one embodiment, it is from 0 to 500 ppm, preferably from 0 to 200 ppm, more preferably from 0 to 100 ppm, and most preferably 1 ppm or less.
  • the contacting of the further organic solvent with the reaction mixture from step a) can be carried out, for example, by adding the reaction mixture containing lithium hexafluorophosphate, a first organic solvent and hydrogen chloride to the initially introduced further organic solvent.
  • any other order of contacting further organic solvent with the reaction mixture of step a) is basically suitable.
  • the contacting can be carried out, for example, such that the reaction mixture from step a) is initially charged and further organic solvent is added.
  • the contacting of the further organic solvent with the reaction mixture from step a) can be carried out, for example, continuously, for example by introducing the further organic solvent or discontinuously, for example by adding in portions, preferably by dropwise addition.
  • Any container known to those skilled in the art of contacting solutions is suitable for contacting.
  • the contacting can be facilitated by introducing mixing energy, for example, by static or non-static mixing elements.
  • the temperature according to step b) can, for example, and preferably from the freezing point to the boiling point of the organic solvent or its low-boiling component used, for example from -45 to 80 ° C, more preferably from 10 to 60 ° C and particularly preferably from 10 to 35 ° C, in particular from 16 to 24 ° C.
  • the pressure during the contacting according to step b) can be, for example, from 100 hPa to 2 MPa, preferably from 900 hPa to 1200 hPa, ambient pressure is particularly preferred.
  • the contacting of the further organic solvent with the reaction mixture from step a) preferably takes place over a period of one second to 48 hours, preferably from 10 seconds to 2 hours, particularly preferably from 30 seconds to 45 minutes and very particularly preferably from 1 minute to 30 minutes.
  • mixing may be achieved by introducing mixing energy, e.g. take place by static or non-static mixing elements.
  • the mixture containing lithium hexafluorophosphate, a first organic solvent and another organic solvent for example, for a period of 10 seconds to 24 Stirred hours, preferably 1 minutes to 12 hours, more preferably 5 minutes to 2 hours and most preferably 10 minutes to 1 hours.
  • step b) leads to a precipitation of the lithium hexafluorophosphate.
  • further contacting with further organic solvent or other organic solvents may be carried out after step b). This has the purpose that in addition to the drying, a further solvent exchange can take place.
  • Separation of the precipitated lithium hexafluorophosphate can be accomplished by any method known to those skilled in the art of solids and liquid separation.
  • the separation can be effected by sedimentation, centrifugation or filtration, for example by pressure filtration or suction filtration.
  • the separation can be carried out, for example, by using a paper filter, polymer filter, a glass frit or a ceramic frit, preferably by a Teflon filter, in particular by a filter with a defined pore size, for example a filter with a pore size of ⁇ 5 ⁇ m, preferably ⁇ 1 ⁇ m, more preferably ⁇ 200 nm.
  • the lithium hexafluorophosphate prepared according to the invention is dissolved in a first organic solvent.
  • the dissolution takes place for example at a temperature of -45 ° C to room temperature, preferably at a temperature of -10 to 10 ° C and more preferably at a temperature of -5 to 5 ° C.
  • This solution is contacted with more organic solvent. This can be done, for example, that the solution of lithium hexafluorophosphate in a first organic Is submitted solvent and further organic solvent is added.
  • the further organic solvent may be charged and the solution of lithium hexafluorophosphate added in a first organic solvent. As already described above, lithium hexafluorophosphate precipitates out as a solid.
  • the precipitated solid can be separated from the first organic solvents and the other organic solvents by the above-described separation methods.
  • the solid lithium hexafluorophosphate can be washed in an alternative embodiment with organic solvent, preferably the other organic solvent described above. Surprisingly, despite the high concentrations of hydrogen chloride in step a), the reaction product lithium hexafluorophosphate contains only small amounts of chloride after completion of step c). Without wishing to be bound by any theory, the Applicant conjectures that the chlorides remain in the first organic solvent. Lithium hexafluorophosphate is less soluble in the other organic solvent and therefore precipitates.
  • Lithium hexafluorophosphate produced according to the invention typically has a content of impurities of 0 to 10,000 ppm, preferably 0 to 5,000 ppm, more preferably 0 to 1, 000 and most preferably 0 to 100 ppm.
  • Examples of typical impurities are hydrolytic decomposition products, in particular lithium difluorophosphate, acids, and metal cations, in particular calcium, chromium, iron, magnesium, molybdenum, cobalt, nickel, cadmium, lead, potassium or sodium and foreign anions, in particular sulfate, hydroxide, bicarbonate and carbonate ,
  • impurities for example acids
  • basic substances for example a base selected from the group consisting of alkaline earth hydroxides, alkaline earth hydrogen carbonates, Alkaline earth carbonates, lithium hydroxide, lithium bicarbonate and lithium carbonate are brought into contact and neutralized.
  • Lithium hexafluorophosphate prepared according to the invention typically has a chloride content of 0 to 100 ppm, preferably 0 to 50 ppm, more preferably 0 to 5 ppm and most preferably 0 to 1 ppm.
  • the chloride content is determined as indicated in the examples.
  • the lithium hexafluorophosphate prepared according to the invention can be further processed, for example, into electrolytes suitable for electrochemical storage devices.
  • the invention further relates to the use of the lithium hexafluorophosphate according to the invention as or for the production of electrolytes for lithium batteries.
  • Electrolytes can be prepared by per se generally known methods by contacting lithium hexafluorophosphate with organic solvent and optionally additives.
  • the invention further relates to a process for preparing electrolytes for lithium batteries, characterized in that the lithium hexafluorophosphate used comprises, according to a process comprising at least the steps a) to c) and optionally d) of the process according to the invention.
  • the electrolytes prepared by the process according to the invention may contain further conductive salts such as, for example, lithium fluorosulfonylimide.
  • the advantage of the invention lies in particular in the efficient procedure and in the small amount of chloride in the lithium hexafluorophosphate prepared according to the invention.
  • Under inert gas condition or inert gas means that the water and oxygen content of the atmosphere is below 1 ppm.
  • the detection limit for chloride ions is 1 ppm.
  • Metal contents were determined by means of a photometric rapid test from Merck (Spectroquant® cuvette test). The photometer used was a Spectroquant Pharo 100 M (Merck).
  • the detection limit for iron is 1.3 ppm.
  • the detection limit for nickel is 2.6 ppm.
  • the detection limit for lead is 2.6 ppm.
  • Examples 1 to 4 were carried out with commercially available phosphorus pentafluoride (99%, but GmbH, CAS 7647-19-0).
  • the phosphorus pentafluoride of Examples 5 and 6 was prepared as follows:
  • Example 3 Preparation of lithium hexafluorophosphate in acetonitrile and subsequent precipitation with toluene
  • Example 4 Preparation of lithium hexafluorophosphate in acetonitrile and subsequent precipitation with toluene and recrystallization
  • Chloride content Below the detection limit
  • Lithium hexafluorophosphate 98.0% by weight
  • EXAMPLE 5 Preparation of Lithium Hexafluorophosphate in Acetonitrile and Subsequent Precipitation with Toluene and Recrystallization 250 ml of acetonitrile and 6.49 g of lithium fluoride were initially charged at room temperature in an argon-filled 500 ml Teflon apparatus without an upstream cooling trap.
  • the gaseous phosphorus pentafluoride / hydrogen chloride mixture (PF 5 / HCl) prepared according to the above procedure was introduced into the resulting suspension until nominally 1 equivalent of phosphorus pentafluoride (calculated from the consumption of PCI 3 , 20 ml consumption) was contained.
  • the resulting reaction mixture was stirred for one hour.
  • the reaction mixture was metered into 500 ml of toluene and stirred for 15 minutes.
  • the precipitated solid was filtered off and blown dry in an argon stream. There was obtained 30.3 g of solid (79% yield). From the solid, a solution (1 1, 8 wt .-% lithium hexafluorophosphate) in dimethyl carbonate / ethylene carbonate (DMC / EC) was prepared.
  • Lithium hexafluorophosphate 80.0% by weight
  • Example 6 Preparation of lithium hexafluorophosphate in acetonitrile and subsequent precipitation with toluene and recrystallization
  • Chloride content Below the detection limit
  • Lithium hexafluorophosphate 99.0% by weight

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Abstract

L'invention concerne un procédé de préparation d'hexafluorophosphate de lithium pauvre en chlorure à partir de fluorure de lithium et de pentafluorure de phosphore, ainsi que son utilisation dans un électrolyte.
EP14716348.9A 2013-04-12 2014-04-10 Électrolyte pauvre en chlorure Withdrawn EP2984038A2 (fr)

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EP20130163517 EP2789583A1 (fr) 2013-04-12 2013-04-12 Electrolyte pauvre en chlorure
PCT/EP2014/057269 WO2014167055A2 (fr) 2013-04-12 2014-04-10 Électrolyte pauvre en chlorure
EP14716348.9A EP2984038A2 (fr) 2013-04-12 2014-04-10 Électrolyte pauvre en chlorure

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NL2020683B1 (en) * 2018-03-29 2019-03-19 The South African Nuclear Energy Corporation Soc Ltd Production of lithium hexafluorophosphate
US11139505B2 (en) * 2018-11-22 2021-10-05 Idemitsu Kosan Co., Ltd. Method for producing solid electrolyte, and electrolyte precursor

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DE2026110C3 (fr) 1969-05-29 1980-02-14 Uss Engineers And Consultants, Inc., Pittsburgh, Pa. (V.St.A.)
US3594402A (en) 1969-05-29 1971-07-20 United States Steel Corp Tetraacetonitrilolithiumhexafluorophosphate and method for the preparation thereof
US5378445A (en) 1993-12-23 1995-01-03 Fmc Corporation Preparation of lithium hexafluorophosphate solutions
DE19614503A1 (de) * 1995-04-12 1996-10-17 Basf Ag Verfahren zur Herstellung von Lithiumhexafluorophosphat
CA2193119C (fr) * 1995-12-14 2001-01-30 Shouichi Tsujioka Solution electrolytique pour piles au lithium et procede de production
US6645451B1 (en) * 1996-06-26 2003-11-11 Solvay Fluor Und Derivate Gmbh Method of preparing inorganic pentafluorides
DE19712988A1 (de) 1996-06-26 1998-01-02 Solvay Fluor & Derivate Herstellung von Lithiumhexafluormetallaten
JP3494344B2 (ja) 1997-12-08 2004-02-09 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の製造方法
DE19805360C1 (de) * 1998-02-12 1999-06-17 Metallgesellschaft Ag Verfahren zur Gewinnung von reinem, grobkristallinen LiPF¶6¶ aus einer Lösung von LiPF¶6¶ in Diethylether
DE19809420A1 (de) * 1998-03-05 1999-09-09 Basf Ag Verfahren zur Herstellung von hochreinen Lithiumsalzen
DE19824984A1 (de) * 1998-06-04 1999-12-09 Basf Ag Verfahren zur Kristallisation von hochreinem LiPF¶6¶ aus organischen Lösungsmitteln

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WO2014167055A2 (fr) 2014-10-16

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