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WO2018201711A1 - Méthode de préparation de bis(fluorosulfonyl)imide de lithium - Google Patents

Méthode de préparation de bis(fluorosulfonyl)imide de lithium Download PDF

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Publication number
WO2018201711A1
WO2018201711A1 PCT/CN2017/114106 CN2017114106W WO2018201711A1 WO 2018201711 A1 WO2018201711 A1 WO 2018201711A1 CN 2017114106 W CN2017114106 W CN 2017114106W WO 2018201711 A1 WO2018201711 A1 WO 2018201711A1
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WO
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Prior art keywords
lithium
under reduced
reduced pressure
fluorosulfonyl
polar solvent
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Ceased
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PCT/CN2017/114106
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English (en)
Chinese (zh)
Inventor
罗乾
巩梦洁
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
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Huizhou Dado New Material Technology Co Ltd
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Publication of WO2018201711A1 publication Critical patent/WO2018201711A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
    • C01B21/086—Compounds containing nitrogen and non-metals and optionally metals containing one or more sulfur atoms

Definitions

  • the invention relates to the technical field of compound preparation, in particular to a preparation method of lithium bisfluorosulfonimide.
  • Fluorosulfonimide and related compounds play an extremely important role in the field of material chemistry and electrochemical energy storage, especially lithium trifluoromethylsulfonimide and lithium bisfluorosulfonimide in lithium ion batteries.
  • Difluorosulfonimide is an important raw material for the preparation of lithium salts and other alkali metal salts and derivatives.
  • Difluorosulfonimide is generally prepared by fluorination of bischlorosulfonimide, and the preparation process of bischlorosulfonimide is mainly Including: 1) preparation of phosphorus pentachloride, sulfamic acid and chlorosulfonic acid (K. Ruff et al, Inorg. Synth.
  • the fluorinating reagent mainly includes arsenic trifluoride, antimony trifluoride, zinc fluoride, anhydrous hydrogen fluoride, antimony trifluoride and the like.
  • the preparation method of lithium bisfluorosulfonimide is as follows: 1) exchange of potassium bisfluorosulfonimide with other lithium salts (for example, lithium perchlorate and lithium tetrafluoroborate) (M. Beran, Polyhedron, 2006, 25, 1292).
  • a lithium bisfluorosulfonimide The preparation method comprises the following steps:
  • fluorosulfonamide is prepared by reacting lithium carbonate with an aqueous solution or an organic solvent to prepare lithium fluorosulfonamide
  • sulfuryl chloride and a fluorinating reagent are reacted to prepare sulfuryl fluoride, the prepared sulfuryl fluoride is directly introduced into a lithium fluorosulfonamide solution, and a tertiary amine is added as an acid binding agent to prepare a difluorosulfonimide ammonium salt;
  • Step 4) Prepare the obtained crude crude product of difluorosulfonimide, add dry polar solvent, stir to dissolve, remove insoluble matter by filtration, remove most of the strong polar solvent under reduced pressure, and add weak polar solvent. The recrystallization operation was carried out, and after filtration, it was dried under reduced pressure to give a product.
  • the organic solvent in the step 1) comprises acetonitrile, acetone, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethyl acetate, propyl acetate, butyl acetate, diethyl ether and methyl t-butyl. At least one of ethers.
  • the fluorinating reagent according to the step 2) comprises at least one of sodium fluoride, potassium fluoride, zinc fluoride and cesium trifluoride, and the stoichiometric molar ratio of the sulfuryl chloride and the fluorinating reagent is 1:2. ⁇ 1:5.
  • the sulfuryl chloride and the fluorinating agent have a stoichiometric molar ratio of 1:2.2 to 1:4 and a reaction temperature of 25 to 80 °C.
  • the tertiary amine in the step 2) comprises at least one of triethylamine, tripropylamine, tributylamine, diisopropylethylamine, pyridine, picoline, and imidazole.
  • the acidic resin described in the step 3) is a strong acid resin of a sulfonic acid type or a weakly acidic resin of a carboxylic acid type.
  • the weakly polar solvent described in the step 4) is dichloromethane, chloroform, n-hexane, cyclohexane, toluene, xylene, chlorobenzene or fluorobenzene.
  • the temperature under reduced pressure drying in the step 4) is 60 to 120 °C.
  • the polar solvent described in the step 5) is dimethyl carbonate, diethyl carbonate, and ethyl carbonate. Ester, ethyl acetate, propyl acetate, butyl acetate, propyl propionate, acetonitrile, propionitrile, acetone, tetrahydrofuran, diethyl ether, methyl tert-butyl ether, propyl ether, dibutyl ether, ethylene glycol dimethyl ether.
  • the weakly polar solvent described in the step 5) is dichloromethane, chloroform, n-hexane, cyclohexane, toluene, xylene, chlorobenzene or fluorobenzene.
  • the preparation method provided by the invention is simple, the reaction time is short, the yield is high, and the metal ion and the anion impurity can be effectively controlled, and the high-purity lithium difluorosulfonimide target product can be prepared.
  • reaction flask 500 mL of the reaction flask, add the lithium fluorosulfonamide prepared in the previous step, add 200 mL of dry acetonitrile and 39.5 g (0.5 mol) of pyridine, ice water bath, and another 500 mL reaction flask to add 135 g (1 mol) of sulfuryl chloride, 200 mL of carbonic acid Ethyl ester, 69.6g (1.2mol) anhydrous potassium fluoride, magnetic stirring, temperature control 80 degrees, the reaction bottle is connected to a -20 degree reflux condenser, the other end of the condensation tube is passed into a fluorosulfonamide lithium / acetonitrile solution, The reaction was stopped after 8 hours. Filtration under reduced pressure gave a clear filtrate, and acetonitrile was removed under reduced pressure to give difluorosulfonimide salt.
  • the bisfluorosulfonimide pyridinium salt is dissolved in water, exchanged with a sulfonic acid type acid resin to obtain an aqueous solution of bisfluorosulfonimide, lithium carbonate is added, the pH is adjusted to be neutral, the solid is removed by filtration, and the aqueous solution is concentrated under reduced pressure. Crystals were precipitated by adding toluene, filtered, and dried under reduced pressure. Further, a dry dimethyl carbonate solvent was added, dissolved, and the insoluble matter was removed by filtration, a large amount of dimethyl carbonate was removed under reduced pressure, and toluene was added to carry out recrystallization, and the obtained solid was dried under reduced pressure to give 65 g of product. (19 F-NMR, 51.4; Cl-ND; SO 4 2- ND; K ⁇ 1ppm; Na ⁇ 5ppm; Mg ⁇ 1ppm; Ca ⁇ 1ppm; Fe ND; Hg ND; Cr ND).
  • reaction flask 500 mL of the reaction flask, add the lithium fluorosulfonamide prepared in the previous step, add 200 mL of dry acetonitrile and 50.5 g (0.5 mol) of triethylamine, ice water bath, and another 500 mL reaction flask to add 135 g (1 mol) of sulfuryl chloride, 200 mL. Diethyl carbonate, 50.4g (1.2mol) anhydrous sodium fluoride, magnetic stirring, temperature control 80 degrees, the reaction bottle is connected to a reflux condenser of -20 degrees, and the other end of the condensation tube is filled with lithium fluorosulfonamide / acetonitrile solution In the reaction, the reaction was stopped after 8 hours. Filtration under reduced pressure gave a clear filtrate, and acetonitrile was removed under reduced pressure to give difluorosulfonimide triethylamine salt.
  • the difluorosulfonimide triethylamine salt is dissolved in water, exchanged with a sulfonic acid type acid resin to obtain an aqueous solution of difluorosulfonimide, lithium hydroxide is added, the pH is adjusted to be neutral, and the solid is removed by filtration and decompressed.
  • the aqueous solution was concentrated, and crystals were precipitated by adding toluene, filtered, and dried under reduced pressure. Further, a dry dimethyl carbonate solvent was added, dissolved, and the insoluble matter was removed by filtration, a large amount of dimethyl carbonate was removed under reduced pressure, and toluene was added to carry out recrystallization, and the obtained solid was dried under reduced pressure to give 63 g of product. (19 F-NMR, 51.6; Cl-ND; SO 4 2- ND; K ⁇ 1ppm; Na ⁇ 5ppm; Mg ⁇ 1ppm; Ca ⁇ 1ppm; Fe ND; Hg ND; Cr ND

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne une méthode de préparation de bis(fluorosulfonyl)imide de lithium. La méthode comprend les étapes consistant à : 1) préparer du fluorosulfonamide de lithium; 2) préparer du fluorure de sulfuryle, introduire le fluorure de sulfuryle dans une solution de fluorosulfonamide de lithium, et ajouter un agent de liaison acide, pour préparer un sel d'ammonium bis(fluorosulfonyl)imide; 3) dissoudre le sel d'ammonium bis(fluorosulfonyl)imide dans une solution aqueuse, et obtenir une solution aqueuse de bis(fluorosulfonyl)imide par résine échangeuse d'ions acide; 4) ajouter du carbonate de lithium pour ajuster la valeur de pH pour obtenir la neutralité, éliminer la matière insoluble par filtration, éliminer la majeure partie de l'eau sous pression réduite, ajouter un solvant organique faiblement polaire pour précipiter un produit brut de bis(fluorosulfonyl)imide, puis sécher le produit brut sous pression réduite; et 5) ajouter un solvant polaire au produit brut de bis(fluorosulfonyl)imide de lithium, agiter la solution pour dissoudre le produit brut, éliminer la matière insoluble par filtration, éliminer le solvant fortement polaire sous pression réduite, ajouter un solvant faiblement polaire pour recristallisation, et filtrer la solution, puis filtrer sous pression réduite pour donner le produit. La méthode de préparation est simple, le temps de réaction est court, le rendement est élevé, et l'ion métallique et les impuretés anioniques peuvent être efficacement contrôlés pour obtenir un produit de pureté élevée.
PCT/CN2017/114106 2017-05-02 2017-11-30 Méthode de préparation de bis(fluorosulfonyl)imide de lithium Ceased WO2018201711A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201710299616.7 2017-05-02
CN201710299616.7A CN107188138B (zh) 2017-05-02 2017-05-02 一种双氟磺酰亚胺锂的制备方法

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Cited By (2)

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US20210178288A1 (en) * 2018-11-16 2021-06-17 Ses Holdings Pte. Ltd. Processes For Removing Reactive Solvent From Lithium Bis(Fluorosulfonyl)Imide (LiFSI) Using Organic Solvents That Are Stable Toward Anodes In Lithium-Ion And Lithium-Metal Batteries
CN117388399A (zh) * 2023-10-25 2024-01-12 山东产研高性能材料技术研究院有限公司 一种高效液相色谱法检测双氯磺酰亚胺缩聚副产物含量的方法

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CN107188138B (zh) * 2017-05-02 2019-05-14 惠州市大道新材料科技有限公司 一种双氟磺酰亚胺锂的制备方法
CN107651654A (zh) * 2017-10-27 2018-02-02 江苏理文化工有限公司 一种以氟盐作为氟化剂的双氟磺酰亚胺锂的制备方法
HUE061383T2 (hu) * 2018-03-27 2023-06-28 Daikin Ind Ltd Elektrolit oldat, elektrokémiai eszköz, lítium-ion másodlagos akkumulátor, modul és vegyület
CN108503670A (zh) * 2018-04-11 2018-09-07 惠州市大道新材料科技有限公司 一种氟磷酰亚胺及其碱金属盐的制备方法
CN110540176B (zh) * 2018-05-28 2021-05-18 浙江蓝天环保高科技股份有限公司 一种提高双氟磺酰亚胺锂纯度的方法
CN108946686A (zh) * 2018-07-31 2018-12-07 九江天赐高新材料有限公司 一种双氟磺酰亚胺锂的制备方法
CN108975292A (zh) * 2018-09-17 2018-12-11 九江天赐高新材料有限公司 一种双氟磺酰亚胺类化合物的制备方法
CN109734061A (zh) * 2019-02-14 2019-05-10 湖南福邦新材料有限公司 一种双氟磺酰亚胺锂的制备方法
CN109928371A (zh) * 2019-04-12 2019-06-25 广州理文科技有限公司 一种双氟磺酰亚胺锂盐的制备方法
CN111591963B (zh) * 2020-06-08 2021-10-26 苏州固锂新能源科技有限公司 一种含氟磺酰亚胺锂的制备方法和纯化工艺
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CN115611244B (zh) * 2021-07-14 2024-02-02 湖南福邦新材料有限公司 一种双氯磺酰亚胺碱金属盐及双氟磺酰亚胺碱金属盐的制备方法
CN114348978A (zh) * 2022-01-29 2022-04-15 宁德时代新能源科技股份有限公司 双氟磺酰亚胺锂及其制备方法、电解液和二次电池
CN114368733A (zh) * 2022-01-29 2022-04-19 宁德时代新能源科技股份有限公司 双氟磺酰亚胺锂及其制备方法、电解液和二次电池
CN114805290A (zh) * 2022-05-12 2022-07-29 常德市大度新材料有限公司 一种硫酸乙烯酯的制备方法
CN114873571B (zh) * 2022-06-28 2023-11-21 河南省氟基新材料科技有限公司 一种双氟磺酰亚胺盐的制备方法
CN115448267B (zh) * 2022-09-19 2023-04-07 安徽新宸新材料有限公司 一种制备双氟磺酰亚胺锂盐的方法
CN115893335B (zh) * 2022-11-14 2025-01-24 常德市大度新材料有限公司 一种双氟磺酰亚胺钠的制备方法
CN116283601A (zh) * 2023-03-16 2023-06-23 浙江中欣氟材股份有限公司 一种双氟磺酰亚胺有机铵盐的制备方法
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CN116409761B (zh) * 2023-06-09 2023-08-18 山东海化集团有限公司 一种双氟磺酰亚胺钠的制备方法
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101747242A (zh) * 2008-11-28 2010-06-23 华中科技大学 双(氟磺酰)亚胺和(全氟烷基磺酰基氟磺酰基)亚胺碱金属盐的制备方法
CN103935970A (zh) * 2014-03-24 2014-07-23 深圳新宙邦科技股份有限公司 双氟磺酰亚胺及其碱金属盐的制备方法
CN104477861A (zh) * 2014-11-24 2015-04-01 中国船舶重工集团公司第七一八研究所 一种双氟磺酰亚胺盐的制备方法
CN104495767A (zh) * 2014-11-21 2015-04-08 湖南有色郴州氟化学有限公司 一种双氟磺酰亚胺锂盐的制备方法
CN105947998A (zh) * 2016-04-29 2016-09-21 金国范 一种利用氮化锂制备双氟磺酰亚胺锂盐的方法
CN106365132A (zh) * 2016-08-31 2017-02-01 中国船舶重工集团公司第七八研究所 一种双氟磺酰亚胺和双氟磺酰亚胺锂的制备方法
CN107188138A (zh) * 2017-05-02 2017-09-22 惠州市大道新材料科技有限公司 一种双氟磺酰亚胺锂的制备方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105923614B (zh) * 2016-04-29 2018-01-09 南京远淑医药科技有限公司 一种利用邻苯二甲酰亚胺制备双氟磺酰亚胺锂盐的方法
CN105905875B (zh) * 2016-04-29 2018-03-16 南京远淑医药科技有限公司 一种利用联氨制备双氟磺酰亚胺锂盐的方法
CN105836719B (zh) * 2016-04-29 2018-06-01 南京远淑医药科技有限公司 一种利用芳香甲基胺合成双氟磺酰亚胺锂盐的方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101747242A (zh) * 2008-11-28 2010-06-23 华中科技大学 双(氟磺酰)亚胺和(全氟烷基磺酰基氟磺酰基)亚胺碱金属盐的制备方法
CN103935970A (zh) * 2014-03-24 2014-07-23 深圳新宙邦科技股份有限公司 双氟磺酰亚胺及其碱金属盐的制备方法
CN104495767A (zh) * 2014-11-21 2015-04-08 湖南有色郴州氟化学有限公司 一种双氟磺酰亚胺锂盐的制备方法
CN104477861A (zh) * 2014-11-24 2015-04-01 中国船舶重工集团公司第七一八研究所 一种双氟磺酰亚胺盐的制备方法
CN105947998A (zh) * 2016-04-29 2016-09-21 金国范 一种利用氮化锂制备双氟磺酰亚胺锂盐的方法
CN106365132A (zh) * 2016-08-31 2017-02-01 中国船舶重工集团公司第七八研究所 一种双氟磺酰亚胺和双氟磺酰亚胺锂的制备方法
CN107188138A (zh) * 2017-05-02 2017-09-22 惠州市大道新材料科技有限公司 一种双氟磺酰亚胺锂的制备方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20210178288A1 (en) * 2018-11-16 2021-06-17 Ses Holdings Pte. Ltd. Processes For Removing Reactive Solvent From Lithium Bis(Fluorosulfonyl)Imide (LiFSI) Using Organic Solvents That Are Stable Toward Anodes In Lithium-Ion And Lithium-Metal Batteries
US12172104B2 (en) * 2018-11-16 2024-12-24 Ses Holdings Pte. Ltd. Processes for removing reactive solvent from lithium bis(fluorosulfonyl)imide (LiFSI) using organic solvents that are stable toward anodes in lithium-ion and lithium-metal batteries
CN117388399A (zh) * 2023-10-25 2024-01-12 山东产研高性能材料技术研究院有限公司 一种高效液相色谱法检测双氯磺酰亚胺缩聚副产物含量的方法

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