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WO2019061802A1 - Procédé de préparation de difluorophosphate de lithium - Google Patents

Procédé de préparation de difluorophosphate de lithium Download PDF

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Publication number
WO2019061802A1
WO2019061802A1 PCT/CN2017/114117 CN2017114117W WO2019061802A1 WO 2019061802 A1 WO2019061802 A1 WO 2019061802A1 CN 2017114117 W CN2017114117 W CN 2017114117W WO 2019061802 A1 WO2019061802 A1 WO 2019061802A1
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WO
WIPO (PCT)
Prior art keywords
lithium difluorophosphate
organic solvent
preparing lithium
polar organic
reaction
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.)
Ceased
Application number
PCT/CN2017/114117
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English (en)
Chinese (zh)
Inventor
韩鸿波
罗乾
董金祥
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.)
Huizhou Dado New Material Technology Co Ltd
Original Assignee
Huizhou Dado New Material Technology Co Ltd
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 Huizhou Dado New Material Technology Co Ltd filed Critical Huizhou Dado New Material Technology Co Ltd
Publication of WO2019061802A1 publication Critical patent/WO2019061802A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/455—Phosphates containing halogen

Definitions

  • the invention relates to the technical field of compound preparation, in particular to a preparation method of lithium difluorophosphate.
  • lithium difluorophosphate improves the structural composition of the interface film by forming a stable passivation film, which is beneficial to reducing the internal resistance of the battery and improving the service life of the battery.
  • the preparation process of lithium difluorophosphate mainly comprises: 1) hydrolysis of lithium hexafluorophosphate to form a mixture of lithium difluorophosphate and lithium hexafluorophosphate, and reaction of lithium hexafluorophosphate and Si-O-Si compound, both of which are difficult to prepare high-purity lithium difluorophosphate 2) the reaction of difluorophosphoric anhydride with lithium fluoride or lithium oxide, the raw material of difluorophosphoric anhydride is relatively rare, and the toxicity is large, and the industrialization cost is high; 3) the reaction of trifluorophosphorus with lithium phosphate or lithium fluoride, The former is required to react at high temperature and high pressure due to low lithium phosphate activity, the latter forms a mixture of lithium difluorophosphate and lithium hexafluorophosphate; 4) the reaction between phosphorus pentafluoride and lithium phosphate, the product is a mixture of lithium hexafluorophosphate
  • the present invention provides a method for preparing lithium difluorophosphate, comprising the following steps:
  • lithium hydroxide is added to a polar organic solvent, and a phosphorus oxyfluoride reaction is introduced under stirring;
  • the polar organic solvent described in the step (1) is acetonitrile, acetone, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethyl acetate, propyl acetate, butyl acetate, diethyl ether and methylate.
  • the fluorinating agent described in the step (1) is one of sodium fluoride, potassium fluoride, zinc fluoride, cesium trifluoride, and hydrogen fluoride.
  • the fluorinating agent described in the step (1) is potassium fluoride and sodium fluoride.
  • the stoichiometric molar ratio of the phosphoryl chloride and the fluorinating reagent described in the step (1) is 1:1.1 to 1:5, and the reaction The temperature is 25 to 80 °C.
  • the stoichiometric molar ratio of the phosphoryl chloride and the fluorinating reagent described in the step (1) is 1:1.5 to 1:4.
  • the polar organic solvent described in the step (2) is dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethyl acetate, propyl acetate, butyl acetate, propyl propionate, acetonitrile, One or more of propionitrile, acetone, tetrahydrofuran, diethyl ether, methyl tert-butyl ether, dipropyl ether, dibutyl ether, ethylene glycol dimethyl ether.
  • the reaction temperature in the step (2) is -5 to 60 °C.
  • the weakly polar solvent described in the step (3) is one or more of dichloromethane, chloroform, n-hexane, cyclohexane, toluene, xylene, chlorobenzene or fluorobenzene.
  • the temperature under reduced pressure drying in the step (3) is 60 to 120 °C.
  • the preparation method of the invention has simple process and low cost, and can obtain high-purity lithium difluorophosphate target product.
  • the technical scheme of the invention is easy to obtain, the cost is low, the production process is simple, the dangerous unit operation involving high temperature and high pressure is not involved, the product is easy to be separated and purified, and the generated hydrogen fluoride by-product is added to the alkali metal carbonate potassium carbonate aqueous solution to prepare the fluorination. Reagent raw materials.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)

Abstract

La présente invention concerne un procédé de préparation de difluorophosphate de lithium, consistant : (1) à préparer du fluorure de phosphoryle par mise en réaction de chlorure de phosphoryle et d'un réactif de fluoration dans un solvant organique polaire; (2) à ajouter de l'hydroxyde de lithium au solvant organique polaire, et à injecter le fluorure de phosphoryle en vue d'une réaction sous agitation; (3) à réaliser une filtration à l'issue de la réaction afin d'obtenir une solution de difluorophosphate de lithium, à ajouter un solvant organique faiblement polaire servant à la recristallisation après la concentration, et à sécher le produit cristallisé sous pression réduite afin d'obtenir un produit. Le procédé fait appel à des matières premières facilement accessibles, a un faible coût et un processus de production simple, ne met pas en œuvre de manipulation d'unité dangereuse impliquant une température élevée et une haute pression, et produit un produit qui est facile à séparer et à purifier et un sous-produit de fluorure d'hydrogène qui peut être ajouté à une solution aqueuse de carbonate de métal alcalin en vue d'un traitement et s'utiliser comme matière première pour préparer des réactifs de fluoration.
PCT/CN2017/114117 2017-09-27 2017-11-30 Procédé de préparation de difluorophosphate de lithium Ceased WO2019061802A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201710889857 2017-09-27
CN201710889857.7 2017-09-27

Publications (1)

Publication Number Publication Date
WO2019061802A1 true WO2019061802A1 (fr) 2019-04-04

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ID=62103412

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2017/114117 Ceased WO2019061802A1 (fr) 2017-09-27 2017-11-30 Procédé de préparation de difluorophosphate de lithium

Country Status (2)

Country Link
CN (1) CN108033435A (fr)
WO (1) WO2019061802A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111115611A (zh) * 2020-03-17 2020-05-08 河南省氟基新材料科技有限公司 一种高纯二氟磷酸锂的制备方法
CN117023549A (zh) * 2023-08-05 2023-11-10 湖北百杰瑞新材料股份有限公司 一种二氟磷酸锂的制备方法
WO2024096273A1 (fr) * 2022-11-04 2024-05-10 주식회사 이브이에스텍 Méthode de production économique de difluorophosphate de lithium

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6428222B2 (ja) * 2014-12-09 2018-11-28 セントラル硝子株式会社 ジフルオロリン酸リチウム粉体の製造方法およびジフルオロリン酸リチウム
CN111646453B (zh) * 2020-06-08 2021-09-10 苏州固锂新能源科技有限公司 一种二氟磷酸锂的制备方法和纯化工艺
CN113636533B (zh) * 2021-08-17 2023-11-10 湖南法恩莱特新能源科技有限公司 一种二氟磷酸锂的制备方法
KR102773206B1 (ko) * 2022-05-31 2025-02-27 이피캠텍 주식회사 리튬이차전지용 디플루오로인산리튬염의 제조방법
WO2023234654A1 (fr) * 2022-05-31 2023-12-07 이피캠텍 주식회사 Méthode de préparation de sel de difluorophosphate de lithium pour batterie secondaire au lithium
KR102521086B1 (ko) * 2022-06-15 2023-04-12 주식회사 에코프로에이치엔 디플루오로인산 리튬의 제조 방법
KR102770609B1 (ko) * 2022-11-04 2025-02-21 주식회사 이브이에스텍 경제적인 디플루오로인산리튬의 제조방법
CN118790971B (zh) * 2024-08-16 2025-08-22 湖北百杰瑞新材料股份有限公司 一种二氟磷酸锂的制备方法

Citations (3)

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Publication number Priority date Publication date Assignee Title
CN101080361A (zh) * 2004-10-19 2007-11-28 三菱化学株式会社 二氟磷酸盐的制造方法、用于二次电池的非水电解液及非水电解液二次电池
CN103052592A (zh) * 2010-08-04 2013-04-17 索尔维公司 从POF3或PF5制造LiPO2F2
CN106882782A (zh) * 2017-03-25 2017-06-23 山东永浩新材料科技有限公司 一种二氟磷酸锂的合成方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2061115B1 (fr) * 2006-08-22 2015-04-01 Mitsubishi Chemical Corporation Lithium difluorophosphate de lithium, solution électrolytique contenant du difluorophosphate de lithium, procédé pour produire du difluorophosphate de lithium, procédé pour produire une solution électrolytique non aqueuse, solution électrolytique non aqueuse, et cellule secon
JP2014528890A (ja) * 2011-08-16 2014-10-30 ソルヴェイ（ソシエテ アノニム） ＬｉＰＯ２Ｆ２とＬｉＰＦ６とを含む混合物の製造
JP6405745B2 (ja) * 2014-06-27 2018-10-17 ダイキン工業株式会社 ジフルオロリン酸リチウムの製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101080361A (zh) * 2004-10-19 2007-11-28 三菱化学株式会社 二氟磷酸盐的制造方法、用于二次电池的非水电解液及非水电解液二次电池
CN103052592A (zh) * 2010-08-04 2013-04-17 索尔维公司 从POF3或PF5制造LiPO2F2
CN106882782A (zh) * 2017-03-25 2017-06-23 山东永浩新材料科技有限公司 一种二氟磷酸锂的合成方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111115611A (zh) * 2020-03-17 2020-05-08 河南省氟基新材料科技有限公司 一种高纯二氟磷酸锂的制备方法
CN111115611B (zh) * 2020-03-17 2022-07-26 河南省氟基新材料科技有限公司 一种高纯二氟磷酸锂的制备方法
WO2024096273A1 (fr) * 2022-11-04 2024-05-10 주식회사 이브이에스텍 Méthode de production économique de difluorophosphate de lithium
CN117023549A (zh) * 2023-08-05 2023-11-10 湖北百杰瑞新材料股份有限公司 一种二氟磷酸锂的制备方法

Also Published As

Publication number Publication date
CN108033435A (zh) 2018-05-15

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