WO2018066896A2 - Procédé de préparation de difluorophosphate de lithium - Google Patents

Procédé de préparation de difluorophosphate de lithium Download PDF

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Publication number
WO2018066896A2
WO2018066896A2 PCT/KR2017/010853 KR2017010853W WO2018066896A2 WO 2018066896 A2 WO2018066896 A2 WO 2018066896A2 KR 2017010853 W KR2017010853 W KR 2017010853W WO 2018066896 A2 WO2018066896 A2 WO 2018066896A2
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WIPO (PCT)
Prior art keywords
lithium
lithium difluorophosphate
formula
mixture
difluorophosphate
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PCT/KR2017/010853
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English (en)
Korean (ko)
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WO2018066896A3 (fr
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임광민
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임광민
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Priority claimed from KR1020160129043A external-priority patent/KR101739936B1/ko
Priority claimed from KR1020170021009A external-priority patent/KR101898803B1/ko
Application filed by 임광민 filed Critical 임광민
Publication of WO2018066896A2 publication Critical patent/WO2018066896A2/fr
Publication of WO2018066896A3 publication Critical patent/WO2018066896A3/fr

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    • 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
    • C01B25/30—Alkali metal phosphates
    • 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
    • C01B25/455—Phosphates containing halogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/12—Organo silicon halides

Definitions

  • the present invention relates to a method for producing lithium difluorophosphate, and more particularly, to produce lithium difluorophosphate, a lithium salt used in an electrolyte for a lithium secondary battery, in a high purity and high yield without a simple and economically dangerous process. And a method for producing lithium difluorophosphate.
  • Table 1 shows a specification for sufficiently exhibiting the performance required in the battery as a material used as an electrolyte additive of a lithium secondary battery.
  • MnXm in the scheme 1 is lithium chloride, lithium bromide, silicon tetrachloride, phosphorus trichloride, acetyl chloride, acetyl bromide, propionyl chloride, oxalyl chloride and the like.
  • lithium difluorophosphate (LiPO 2 F 2 ) is prepared by reacting lithium hexafluorophosphate (LiPF 6 ) with water and a halogen compound as a starting material.
  • lithium difluorophosphate should be free of impurities such as inorganic salts because lithium difluoride is used in the electrolyte.
  • the method according to Scheme 2 is a method for producing lithium difluorophosphate by heating a variety of siloxane and lithium hexafluorophosphate in the absence of water.
  • Lithium difluorophosphate manufacturing method has the advantage that does not generate acid gas and inorganic salts, but the price of siloxane is expensive and the reactivity is low, the reaction does not proceed at room temperature, and also to about 60 °C In the case of the heating reaction, insoluble impurities are generated in a large amount, which is not suitable for use as an electrolyte of a lithium secondary battery.
  • An object of the present invention is to solve the problems of the prior art as described above, and to produce lithium difluorophosphate, which is a lithium salt used in an electrolyte for a lithium secondary battery, in a high purity and high yield without a simple and economically dangerous process, It is to provide a method for producing lithium difluorophosphate.
  • the present invention comprises the steps of preparing a first mixture by mixing a lithium hexafluorophosphate and a solvent; Preparing a second mixture by adding water to the first mixture; Adding an organic silyl halide mixture to the second mixture, followed by stirring to react; It provides a method for producing lithium difluorophosphate comprising the step of heating the reaction product, depressurizing and then filtration to prepare a lithium difluorophosphate (lithium difluorophosphate) represented by the following formula (1).
  • the present invention comprises the steps of reacting by adding water (H 2 O) and the organosylsilyl halide at the same time to the lithium hexafluorophosphate solution; Or it provides a method for producing lithium difluorophosphate represented by the following formula (1) comprising the step of adding water to the lithium hexafluoro phosphate solution and then organosyl halide to react sequentially.
  • the method for producing lithium difluorophosphate according to the present invention is economical by using a mixture of organosilyl halides in place of the expensive siloxanes used in the conventional production of lithium difluorophosphate, and is a high-purity difluoro having a low content of various impurities. Lithium phosphate can be obtained, and there is an advantage of ensuring safety due to less corrosiveness during the process.
  • the conventional manufacturing method has to remove impurities by an additional process due to the occurrence of unavoidable by-products, such as chloride or insoluble content, the present invention can produce a high yield and high purity lithium difluorophosphate without a special purification by a simple process There is an advantage.
  • the inventors of the present invention can reduce the content of chloride impurities generated as a reaction by-product by sequentially adding water and organosilyl halide to the lithium hexafluorophosphate solution, thereby producing high yield and high purity lithium difluorophosphate. Revealed to complete the present invention.
  • the present invention comprises the steps of preparing a first mixture by mixing a lithium hexafluorophosphate and a solvent; Preparing a second mixture by adding water to the first mixture; Adding an organic silyl halide mixture to the second mixture, followed by stirring to react; It provides a method for producing lithium difluorophosphate comprising the step of heating the reaction product, depressurizing and then filtration to prepare a lithium difluorophosphate (lithium difluorophosphate) represented by the following formula (1).
  • lithium difluorophosphate of the present invention may be prepared as in Scheme 3 below.
  • the method for preparing lithium difluorophosphate according to the present invention is made by using lithium hexafluorophosphate (LiPF 6 ) as a starting material and reacting with water and organosilyl halides in an appropriate ratio and order. Lithium phosphate can be prepared.
  • LiPF 6 lithium hexafluorophosphate
  • the organosilyl halide mixture may be a mixture of organosilyl halides represented by Formulas 2 and 3 below, but is not limited thereto.
  • R 1 to R 5 are the same as or different from each other, C 1 to C 10 straight or branched alkyl, C 2 to C 10 straight or branched alkenyl or aryl,
  • X 1 to X 3 are the same as or different from each other, and are chlorine (Cl), bromine (Br), or iodine (I).
  • R 1 to R 5 may be any one selected from the group consisting of methyl, ethyl, propyl, and vinyl, but is not limited thereto.
  • the organosilyl halide represented by Formula 2 is preferably trimethylsilyl chloride
  • the organosilyl halide represented by Formula 3 is preferably dimethylsilyl dichloride.
  • Dimethylsilyl dichloride is cheaper than trimethylsilyl chloride and can use only 1/2 equivalent of trimethylsilyl chloride equivalent, which is economical when used in combination with trimethylsilyl chloride and dimethylsilyl dichloride. Excellent in terms of corrosiveness and degradability.
  • the organosilyl halide mixture is an organic silyl halide represented by Formula 2 relative to lithium hexafluorophosphate in a ratio of 0.02 to 2.0 equivalents, and an organosilyl halide represented by Formula 3 relative to lithium hexafluorophosphate is 0.99 to 2.08. It may be an equivalent ratio, but is not limited thereto.
  • the organosilyl halide is preferably added in an amount of 3.98 to 4.20 equivalents in a halide equivalent ratio of total organosilyl halide to lithium hexafluorophosphate.
  • the organosilyl halide represented by Formula 2 is 1 mol per mol of lithium hexafluorophosphate
  • the organosilyl halide represented by Formula 3 reacts with 2 mol per mol of lithium hexafluorophosphate.
  • Low Phosphate It is desirable to adjust between 3.98 and 4.20 equivalent ratios in total.
  • the organosilyl halide represented by lithium hexafluoro phosphate reacts directly and there is a problem that impurities contaminated with lithium monofluoromonophosphate are generated.
  • the amount of Cl impurity including the same should be 100 ppm or less, preferably 20 ppm or less, but depending on the conditions, there are problems ranging from several thousand ppm to several hundred ppm in lithium difluorophosphate.
  • organosilyl halide represented by Formula 3 can be suppressed to some extent by using the organosilyl halide represented by Formula 3 to solve the above problem.
  • organosilyl halide represented by Formula 3 since C 1 to C 10 linear or branched alkyl, C 2 to C 10 linear or branched alkenyl or aryl groups in the intramolecular silicon, This is because the number of the organosilyl halides represented by the general formula (3) is smaller than that of the organosilyl halide.
  • there are two halogen atoms it is more difficult for the halogen elements to be released as anions in the molecule.
  • halogen anions may be released and react with lithium hexafluorophosphate to significantly reduce the probability of producing halogen-bound impurities.
  • organosilyl halide represented by the formula (3) when using the organosilyl halide represented by the formula (3) alone, in the presence of a small amount of water to form a siloxane oligomer to a lower polymer may also be a factor of lowering the purity because insoluble impurities are generated.
  • dimethylsilyldichloride is used alone in the organosilyl halide represented by Formula 3, the yield of lithium difluorophosphate drops to 85.0% or less, and the purity falls to 99.0% or less, requiring an additional purification process. have.
  • Such a phenomenon is because two halogens are attached to the organosilyl halide molecule represented by Chemical Formula 3 so that the oligomer or the polymer can be formed.
  • the organosilyl halide represented by the formula (2) has only one halogen in the molecule, so that the reaction can proceed to the oligomer or the polymer, thus preventing the generation of impurities that lower the purity.
  • the use of the organosilyl halide represented by the formula (2) and the organosilyl halide represented by the formula (3) is higher than that of using each alone, and the purity, Cl content, HF content, yield, and economic efficiency of lithium difluorophosphate are high. You can see the excellent.
  • the equivalent ratio of the organosyl silyl halide represented by the formula (3) and the organosyl silyl halide represented by the formula (2) is 1: 2 to 1: 0.01, and considering the economic efficiency and purity, the optimum equivalent ratio is 1: It is preferable that it is 0.5-1: 0.02.
  • the reacting may be performed by adding an organic silyl halide mixture to the second mixture, followed by stirring at 40 to 80 rpm and reaction at ⁇ 10 to 60 ° C., but is not limited thereto.
  • reaction conditions such as said reaction temperature
  • the upper limit of reaction temperature becomes like this.
  • it is 60 degreeC, More preferably, it is 40 degrees C or less, and a minimum is preferable.
  • it is -10 degreeC, More preferably, it is 0 degreeC or more. If it exceeds 60 ° C, decomposition of LiPF 6 occurs and PF 5 is generated to decompose the solvent, which is not preferable, and at a temperature lower than -10 ° C, the progress of the reaction is not economical.
  • the present invention comprises the steps of reacting by adding water (H 2 O) and the organosylsilyl halide at the same time to the lithium hexafluorophosphate solution; Or it provides a method for producing lithium difluorophosphate represented by the following formula (1) comprising the step of adding water to the lithium hexafluoro phosphate solution and then organosyl halide to react sequentially.
  • lithium difluorophosphate of the present invention may be prepared as in Scheme 4 below.
  • the lithium difluorophosphate represented by Chemical Formula 1 may be prepared by reacting water with an organosilyl halide using lithium hexafluorophosphate (LiPF 6 ) as a starting material. .
  • the organosilyl halide may be an organosilyl halide represented by Formula 4 below, but is not limited thereto.
  • n is an integer of 1 to 3
  • m is an integer of 1 to 3
  • R is C 1 ⁇ C 10 linear or branched alkyl, C 2 to C 10 linear or branched alkenyl or Aryl
  • X may be chlorine (Cl), bromine (Br), or iodine (I), and in particular, the use of trimethylsilyl chloride as the organosilylide halide is preferred in terms of stability, corrosiveness and degradability.
  • the organosilyl halide may be added in an amount of 1.33 to 4.0 equivalents to lithium hexafluorophosphate, in particular, R 1 SiX 3 is preferably 1.33 equivalents, R 2 SiX 2 is 2.0 equivalents, and R 1 SiX 3 is preferably 4.0 equivalents. Do.
  • the order of addition of water (H 2 O) and organosilyl halides is particularly important in the reaction. It is preferable to add (i) water (H 2 O) to the lithium hexafluorophosphate solution, and then add organosilyl halide or (ii) simultaneously add water (H 2 O) and organosilyl halide. .
  • reaction conditions such as said reaction temperature
  • the upper limit of reaction temperature becomes like this.
  • it is 80 degreeC, More preferably, it is 60 degrees C or less, and a minimum is preferable.
  • it is -10 degreeC, More preferably, it is 0 degreeC or more. It is not preferable to decompose LiPF 6 when it exceeds 80 deg. C to generate PF 5 to decompose the solvent, and it is not economical because the progress of the reaction is slow at a temperature lower than -10 deg.
  • the temperature of the reactant was raised to 25 ° C., and the generated acid gas was removed under reduced pressure, and then, the produced lithium difluorophosphate was filtered and dried to obtain the lithium difluorophosphate of the present invention (Formula 1). It can manufacture.
  • the solvent may be in an amount of 0.5 to 100 equivalents based on lithium hexafluorophosphate, but is not limited thereto.
  • the solvent may be any one selected from the group consisting of diethyl ether, diisopropyl ether, and methyl t-butyl ether; Dimethoxyethane and alkoxyethanes of diethoxyethane; Ester, which is any one selected from the group consisting of methyl acetate, ethyl acetate, propyl acetate, and butyl acetate; Nitriles which are any one selected from the group consisting of acetonitrile, propionitrile, and butyronitrile; Hydrocarbons which are any one selected from the group consisting of pentane, hexane, and heptane; Alcohols which are any one selected from the group consisting of methanol, ethanol, propanol, and butanol; Ketones which are any one selected from the group consisting of acetone, methyl ethyl ketone, and methyl isopropyl ketone; And carbonates which are any one selected from
  • the water may be in a ratio of 1.00 to 2.05 equivalents relative to lithium hexafluorophosphate, but is not limited thereto.
  • the water may be added in reverse amount from the required amount of lithium difluorophosphate to determine the amount of water, but from 1.90 to Lithium fluorophosphate. It is preferable to use water in a 2.05 equivalent ratio, or to use it in 1.0 to 3.0 equivalent ratio, especially 2.0 equivalent ratio.
  • the first mixture was cooled to 5 ° C. using an ice bath, and 21.3 g of water (H 2 O) was added to prepare a second mixture.
  • reaction mixture was gradually heated up to 20 ° C, and the generated hydrochloric acid gas, dimethylsilyldifluoride, and trimethylsilylfluoride were removed under reduced pressure to 30 mmHg.
  • the prepared salt was filtered off with a filter paper and then washed with 21 g of dimethylcarbonate.
  • the washed salt was recovered and dried to 50 ° C. or less to obtain a lithium powder, difluorophosphate compound (yield: 91.0%, purity: 99.7%, Cl content: 8 ppm).
  • a lithium powder of difluorophosphate a white powder, was obtained under the same conditions as in Example 1 except that 159.81 g of dimethylsilyldichloride and 0.64 g of trimethylsilyl chloride were added to the second mixture (yield: 83.0%, purity). : 98.3%, Cl content: 8 ppm).

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

La présente invention concerne un procédé de préparation de difluorophosphate de lithium, et concerne plus particulièrement un procédé de préparation de difluorophosphate de lithium, qui permet une préparation simple et économique de difluorophosphate de lithium, qui est un sel de lithium utilisé dans un électrolyte d'une batterie secondaire au lithium, présentant un haut niveau de pureté et à haut rendement sans traitement dangereux. En utilisant un mélange d'halogénure de silyle organique plutôt que du siloxane coûteux utilisé dans la préparation du difluorophosphate de lithium, le procédé de préparation de difluorophosphate de lithium selon la présente invention est économique, permet d'obtenir du difluorophosphate de lithium de haute pureté présentant de faibles quantités d'impuretés diverses, et assure la sécurité du fait d'une faible corrosivité lors du traitement. De plus, la présente invention permet la préparation de difluorophosphate de lithium à haut rendement et de haute pureté au moyen d'un traitement simple sans raffinage particulier, tandis que, dans des procédés de préparation existants, des sous-produits inévitables sont générés, tels que du chlorure ou des matières insolubles, des impuretés devant ainsi être éliminées par le biais d'un traitement supplémentaire. En outre, en faisant réagir un composé bis(chlorosulfonyl)amine, qui est un matériau de départ, avec de l'eau (H2O) et un halogénure de silyle organique, la présente invention permet de résoudre les problèmes de l'état de la technique et de rendre possible une préparation simple et économique de difluorophosphate de lithium de haute pureté et à haut rendement sans traitement dangereux.
PCT/KR2017/010853 2016-10-06 2017-09-28 Procédé de préparation de difluorophosphate de lithium WO2018066896A2 (fr)

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KR1020160129043A KR101739936B1 (ko) 2016-10-06 2016-10-06 디플루오로인산리튬의 신규 제조방법
KR10-2016-0129043 2016-10-06
KR1020170021009A KR101898803B1 (ko) 2017-02-16 2017-02-16 디플루오로인산리튬의 제조방법
KR10-2017-0021009 2017-02-16

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CN108793118A (zh) * 2018-08-13 2018-11-13 合肥天徽新材料有限公司 一种二氟磷酸锂的生产装置及生产方法
CN111224164A (zh) * 2019-12-13 2020-06-02 九江天赐高新材料有限公司 一种二氟磷酸锂的制备方法
CN114634170A (zh) * 2020-12-15 2022-06-17 江苏国泰超威新材料有限公司 一种二氟磷酸锂的制备方法
CN115215316A (zh) * 2021-04-15 2022-10-21 浙江省化工研究院有限公司 一种二氟磷酸锂的制备方法
CN115321510A (zh) * 2022-08-30 2022-11-11 珠海正杏新材料科技有限公司 一种二氟磷酸锂的制备方法
CN116443843A (zh) * 2023-05-06 2023-07-18 珠海市赛纬电子材料股份有限公司 一种废旧电解液回收方法

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JP4650627B2 (ja) * 2005-09-14 2011-03-16 信越化学工業株式会社 環状カーボネート変性シロキサン及びその製造方法並びに非水電解液、二次電池及びキャパシタ
KR101539780B1 (ko) * 2006-08-22 2015-07-27 미쓰비시 가가꾸 가부시키가이샤 2 불화 인산 리튬, 2 불화 인산 리튬 함유 전해액, 2 불화 인산 리튬의 제조 방법, 비수계 전해액의 제조 방법, 비수계 전해액 및 그것을 사용한 비수계 전해액 2 차 전지
JP5277550B2 (ja) * 2007-03-12 2013-08-28 セントラル硝子株式会社 ジフルオロリン酸リチウムの製造方法及びこれを用いた非水電解液電池
WO2012016924A1 (fr) * 2010-08-04 2012-02-09 Solvay Sa Fabrication de lipo2f2 à partir de pof3 ou de pf5
JP5687792B2 (ja) * 2013-06-07 2015-03-18 ステラケミファ株式会社 ジフルオロリン酸塩の製造方法

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CN108793118A (zh) * 2018-08-13 2018-11-13 合肥天徽新材料有限公司 一种二氟磷酸锂的生产装置及生产方法
CN111224164A (zh) * 2019-12-13 2020-06-02 九江天赐高新材料有限公司 一种二氟磷酸锂的制备方法
CN111224164B (zh) * 2019-12-13 2022-07-15 九江天赐高新材料有限公司 一种二氟磷酸锂的制备方法
CN114634170A (zh) * 2020-12-15 2022-06-17 江苏国泰超威新材料有限公司 一种二氟磷酸锂的制备方法
CN115215316A (zh) * 2021-04-15 2022-10-21 浙江省化工研究院有限公司 一种二氟磷酸锂的制备方法
CN115215316B (zh) * 2021-04-15 2023-09-15 浙江省化工研究院有限公司 一种二氟磷酸锂的制备方法
CN115321510A (zh) * 2022-08-30 2022-11-11 珠海正杏新材料科技有限公司 一种二氟磷酸锂的制备方法
CN116443843A (zh) * 2023-05-06 2023-07-18 珠海市赛纬电子材料股份有限公司 一种废旧电解液回收方法

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