WO2024008206A1 - Preparation method for lithium difluorophosphate - Google Patents

Preparation method for lithium difluorophosphate Download PDF

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WO2024008206A1
WO2024008206A1 PCT/CN2023/111387 CN2023111387W WO2024008206A1 WO 2024008206 A1 WO2024008206 A1 WO 2024008206A1 CN 2023111387 W CN2023111387 W CN 2023111387W WO 2024008206 A1 WO2024008206 A1 WO 2024008206A1
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anhydrous
reaction
diphosphate
preparation
lithium
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PCT/CN2023/111387
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French (fr)
Chinese (zh)
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贾国文
朱振涛
王卫江
马立军
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山东海科创新研究院有限公司
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Publication of WO2024008206A1 publication Critical patent/WO2024008206A1/en

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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
    • C01B25/455—Phosphates containing halogen
    • 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 application belongs to the technical field of lithium battery additive preparation, and particularly relates to a preparation method of lithium difluorophosphate.
  • the synthesis of lithium salt additives is usually prepared by using lithium hexafluorophosphate as the front-end material.
  • the synthesis of lithium difluorophosphate is generated by the reaction of lithium hexafluorophosphate and lithium carbonate or lithium hexafluorophosphate and siloxane.
  • the cost remains high.
  • the development of a new synthesis process for lithium difluorophosphate has attracted widespread attention in the industry, and the process route is also deliberately avoiding high-priced lithium sources such as lithium hexafluorophosphate.
  • lithium difluorophosphoric acid is prepared by directly reacting difluorophosphoric acid with a lithium source.
  • difluorophosphoric acid itself is difficult to purchase.
  • Patent CN114604844A first esterifies phosphorus oxychloride and a monohydric alcohol to obtain dichlorophosphate; then fluorinates dichlorophosphate with a fluorinating reagent to obtain difluorophosphate; and finally utilizes difluorophosphate Lithium difluorophosphate is prepared by lithiation reaction between phosphate ester and lithiation reagent.
  • phosphorus oxychloride is highly corrosive and volatile, which makes it relatively dangerous.
  • phosphorus oxychloride is extremely active, and the possibility of obtaining by-products is very high. There are certain uncontrollable risks in scaling up production. Using potassium fluoride for fluorination involves the risk of introducing impurity potassium ions, and the reaction in this method takes a long time.
  • this application provides a preparation method of lithium difluorophosphate, which includes the following steps:
  • the molar mass ratio of ethylene glycol and the catalyst p-toluenesulfonic acid in step 1) is 1 mol:0.05g ⁇ 0.1g; the molar ratio of ethylene glycol and phosphoric acid is 1: 2.0 ⁇ 2.5.
  • the feed rate of the mixed solution of ethylene glycol and the catalyst p-toluenesulfonic acid in step 1) is 30-40ml/min, and the feed rate of phosphoric acid is 70-100ml/min; in the microchannel reaction When the reaction is carried out in the vessel, the reaction temperature is 40 to 50°C.
  • the temperature during distillation and purification in step 2) is 90-120°C
  • the vacuum degree is 30-100 Pa
  • the reflux ratio is 4-6.
  • the anhydrous fluorinating agent in step 3) is anhydrous ammonium fluoride and/or anhydrous ammonium bifluoride; the activation method of the anhydrous fluorinating agent is anhydrous fluorination
  • the agent is ball milled and passed Sieve; the rotation speed of the ball mill is 500-800 rpm; the aperture of the sieve used for screening is 200-500 mesh.
  • the molar ratio of the activated anhydrous fluorinating agent to the diphosphate in step 3) is 4.5-5.0:1; the molar mass of the diphosphate and antimony pentafluoride The ratio is 1 mol: 0.03 ⁇ 0.08g; the anhydrous organic solvent is one of anhydrous tetrahydrofuran, anhydrous acetonitrile, and anhydrous N, N-dimethylformamide, and the added amount of the anhydrous organic solvent is per mole Add 1L to 2L anhydrous organic solvent to the diphosphate.
  • the dropping rate of the diphosphate in step 3) is 0.5 to 2 hours per mole of liquid, the temperature of the reaction is 85 to 100°C, and the reaction time after the dropwise addition is completed is 3 ⁇ 5h.
  • the lithium source in step 4) is lithium hydroxide, and the molar ratio of the bisdifluorophosphate to the lithium source is 1:2.1 ⁇ 3; the bisdifluorophosphate and The molar volume ratio of anhydrous ethylene glycol dimethyl ether is 1mol:2.5 ⁇ 3L.
  • the dropping rate of the bisdifluorophosphate is 2 to 3 hours per mole; the reaction temperature is 50 to 70°C, and the reaction is carried out after the dropwise addition is completed The time is 1 ⁇ 2h.
  • the purification method is to sequentially filter, rotary evaporate, recrystallize and suction filtrate the reaction product; the rotary evaporated
  • the conditions are 100 ⁇ 120°C and the vacuum degree is -0.08 ⁇ -0.1MPa; the drying temperature is 80 ⁇ 120°C and the vacuum degree is 30 ⁇ 80Pa.
  • the preparation method of lithium difluorophosphate provided in at least one embodiment of the present application first uses ethylene glycol and phosphoric acid to perform an esterification reaction in a microchannel reactor under the action of an esterification reaction catalyst to generate a diphosphate ester, and then The diphosphate is fluorinated using a highly active fluorinating agent to become bisdifluorophosphate. Finally, the bisdifluorophosphate is reacted with a lithium source to obtain high-purity difluorophosphate Lithium Products.
  • the raw materials ethylene glycol, phosphoric acid, ammonium fluoride and ammonium bifluoride used in this application are all bulk products with high safety factor and low cost.
  • the preparation method of lithium difluorophosphate provided in at least one embodiment of the present application is efficient, green, and safe.
  • the reaction raw materials are low in cost and easy to obtain, and the prepared product has high purity and high yield.
  • the embodiments of the present application provide a method for preparing lithium difluorophosphate, which includes the following steps:
  • a mixture of ethylene glycol, catalyst p-toluenesulfonic acid, and phosphoric acid were separately introduced into a microchannel reactor for reaction to obtain a mixture containing diphosphate.
  • the molar mass ratio of the ethylene glycol to the catalyst p-toluenesulfonic acid is 1mol:0.05g ⁇ 0.1g; the molar ratio of ethylene glycol and phosphoric acid is 1:2.0 ⁇ 2.5.
  • nitrogen gas is first used to purge the reactor pipeline. After the purging is completed, the temperature is raised to the reaction temperature before the materials are introduced. This operation is used to drain the air and impurities in the pipeline to avoid affecting the reaction.
  • the reaction temperature is 40-50°C.
  • the feed rate of the mixed liquid of ethylene glycol and catalyst p-toluenesulfonic acid is 30-40 ml/min
  • the feed rate of phosphoric acid is 70-100 ml/min.
  • the present application After obtaining the diphosphate-containing mixture, the present application performs distillation and purification on the diphosphate-containing mixture to obtain the diphosphate.
  • the temperature of the distillation and purification is 90-120°C
  • the vacuum degree is 30-100 Pa
  • the reflux ratio is 4-6.
  • after obtaining the diphosphate it is placed under sealed conditions when not in use.
  • the activated anhydrous fluorinating agent, antimony pentafluoride and anhydrous organic solvent are mixed, the diphosphate is added dropwise, and the reaction is carried out after the dropwise addition is completed to obtain the bisdifluorophosphate.
  • the anhydrous fluorinating agent is anhydrous ammonium fluoride and/or anhydrous ammonium bifluoride;
  • the activation method of the anhydrous fluorinating agent is ball milling and sieving the anhydrous fluorinating agent;
  • the rotation speed of the ball mill is 500-800 rpm;
  • the dropping rate of the diphosphate is 0.5 to 2 hours per mole of liquid.
  • the reaction temperature is 85 to 100°C, and the reaction time after the dropwise addition is completed is 3 to 5 hours.
  • the reactants can be better dispersed, and with the stirring of the reactor, the esters can fully contact with the excess anhydrous fluorinating agent, thereby making the fluorination efficiency more sufficient and ensuring that It is possible that many esters are fully fluorinated.
  • the molar ratio of the activated anhydrous fluorinating agent to the diphosphate is 4.5-5.0:1; the molar mass ratio of the diphosphate to antimony pentafluoride is 1 mol: 0.03-0.08 g; the anhydrous organic solvent is one of anhydrous tetrahydrofuran, anhydrous acetonitrile, and anhydrous N, N-dimethylformamide. The amount of the anhydrous organic solvent added is 1L to 2L per mole of diphosphate. Anhydrous organic solvent.
  • the use of the above-mentioned anhydrous organic solvent can completely eliminate the influence of moisture on the reaction.
  • certain phosphate esters come into contact with water, they may decompose under the catalysis of other substances, and if the fluorinating agent comes into contact with water, Due to the effect of high temperature, the fluorinating agent will be more likely to decompose and turn into toxic and harmful substances such as hydrofluoric acid or ammonia.
  • the above-mentioned anhydrous organic solvents are substances with low boiling points, so the temperature can be kept below the boiling temperature. , to prevent overheating and decomposition of substances.
  • the bisdifluorophosphate is a difluorophosphoric anhydride substance, which is disclosed in patent JP2008287965.
  • the cost of difluorophosphoric anhydride used in this patent is relatively high.
  • ethylene glycol and phosphoric acid are used as raw materials to prepare bisdifluorophosphoric acid ester. The raw material cost is low and the reaction is simple, making it more suitable for industrial production.
  • this application adds bisdifluorophosphate dropwise to the mixture of lithium source and anhydrous ethylene glycol dimethyl ether. After the dropwise addition is completed, the reaction proceeds to obtain lithium difluorophosphate. In some embodiments, the obtained bisdifluorophosphate is subjected to distillation and purification before reaction.
  • the temperature of the distillation and purification is 120-150°C
  • the vacuum degree is 10-30 Pa
  • the reflux ratio is 4-6.
  • the dropping rate of the bisdifluorophosphate is 2 to 3 hours per mole; so The temperature of the reaction is 50 to 70°C, and the reaction time after the dropwise addition is completed is 1 to 2 hours.
  • the lithium source is lithium hydroxide; the molar ratio of the bisdifluorophosphate to the lithium source is 1:2.1 ⁇ 3; the bisdifluorophosphate and anhydrous ethylene glycol dimethyl The molar volume ratio of ether is 1mol:2.5 ⁇ 3L.
  • lithium difluorophosphate is directly synthesized by reacting dihalogen phosphate ester with a lithium source, but dihalogen phosphate itself is not a bulk product and is difficult to purchase.
  • bisdifluorophosphate is prepared by fluorination of diphosphate, which is easy to prepare, and the production efficiency of bisdifluorophosphate is higher than that of difluorophosphate. This is because bisdifluorophosphate has double-terminal properties.
  • the reaction activity of functional groups is higher than that of difluorophosphate, and because of its larger molecular structure, it can break bonds well and promote the further formation of the reaction.
  • purification and drying are also included.
  • the purification method includes filtering, rotary evaporation, recrystallization and suction filtration of the reaction product in sequence.
  • the rotary evaporation conditions are 100 to 120°C, and the vacuum degree is -0.08 to -0.1MPa.
  • the solvent for recrystallization is methylene chloride and/or n-hexane; the added amount of the solvent for recrystallization is 500-800 ml of solvent per mole of bisdifluorophosphate.
  • the drying temperature is 80-120°C, and the vacuum degree is 30-80 Pa.
  • reaction equation for preparing lithium difluorophosphate is as follows:
  • the pump is injected into the microchannel reactor for reaction (the mixed liquid is fed from the inside at a feeding rate of 30 ml/min; phosphoric acid is fed from the outside at a feeding rate of 80 ml/min) to obtain a mixture containing diphosphate, phosphate, and water. and other impurities in the reaction solution.
  • the reaction liquid was subjected to distillation and purification (distillation conditions were 110°C, vacuum degree 30Pa, reflux ratio selected 6) to obtain a diphosphate yield of 89.4% and a purity of 99.1%. Seal the diphosphate and set aside.
  • reaction product After the reaction product is cooled, it is rectified at 120°C, 10 Pa, and reflux ratio 4 to obtain the bisdifluorophosphate product with a yield of 92.8% and a purity of 99.4%.
  • the bisdifluorophosphate is dehydrated. save.
  • the product index testing methods are as follows:
  • Purity test Use the external standard method of ion chromatography to conduct the purity test.
  • the mixed liquid is fed from the inside, the feeding speed is 40ml/min; the phosphoric acid is fed from the outside, the feeding speed is 100ml/min), and the mixture containing diphosphate, phosphate, water and Reaction solution containing other impurities.
  • the reaction solution was subjected to distillation and purification (distillation conditions were 110°C, vacuum degree 30Pa, reflux ratio selected 5) with a product yield of 91.4% and a purity of 99.3% to obtain a diphosphate, which was sealed and placed for later use.
  • reaction product After the reaction product is cooled, it is rectified at 150°C, 30 Pa, and reflux ratio 4 to obtain the bisdifluorophosphate product with a yield of 94.1% and a purity of 99.2%, and the bisdifluorophosphate is dehydrated. save.
  • the crude product is dried in a vacuum oven (drying conditions are 100°C, vacuum degree is 50Pa), and finally a pure lithium difluorophosphate product is obtained, with a product purity of 99.95%, a comprehensive product yield of 81.8%, and a moisture content of 7.4ppm.
  • the mixed liquid is fed from the inside, the feeding speed is 35ml/min; the phosphoric acid is fed from the outside, the feeding speed is 90ml/min), and the mixture containing diphosphate, phosphate, water and Reaction solution containing other impurities.
  • the reaction solution was subjected to distillation and purification (distillation conditions were 90°C, vacuum degree 100Pa, reflux ratio selected 4) to obtain a diphosphate product with a yield of 90.2% and a purity of 99.5%.
  • the diphosphate was sealed and placed for later use.
  • reaction product After the reaction product is cooled, it is rectified at 120°C, 10 Pa, and reflux ratio 4 to obtain the bisdifluorophosphate product with a yield of 93.6% and a purity of 99.3%.
  • the bisdifluorophosphate is dehydrated. save.
  • the crude product was dried in a vacuum oven (drying condition: 100°C, vacuum degree: 50Pa), and finally a pure lithium difluorophosphate product was obtained, with a product purity of 99.89%, a product yield of 82.18%, and a moisture content of 7.9ppm.
  • Example 1 The difference from Example 1 is that the anhydrous fluorinating agent used does not undergo activation and directly uses reagent grade raw materials.
  • the other operating steps are exactly the same as Example 1.
  • the specific operations are as follows:
  • the mixed liquid is fed from the inside, the feeding speed is 30ml/min; the phosphoric acid is fed from the outside, the feeding speed is 80ml/min), and the mixture containing diphosphate, phosphate, water and Reaction solution containing other impurities.
  • the reaction solution was subjected to distillation and purification (distillation conditions were 110°C, vacuum degree 30Pa, reflux ratio selected 6) to obtain a diphosphate product with a yield of 90.1% and a purity of 99.2%.
  • the diphosphate was sealed and placed for later use.
  • Example 1 The difference from Example 1 is that the diphosphate ester is prepared in a kettle reactor, and other operating steps are exactly the same as Example 1.
  • the specific operations are as follows:
  • the reaction solution was subjected to distillation and purification (distillation conditions were 110°C, vacuum degree 30Pa, reflux ratio selected 6) to obtain a diphosphate product with a yield of 72.6% and a purity of 99.1%.
  • the diphosphate was sealed and placed for later use.
  • reaction product After the reaction product is cooled, it is distilled under the conditions of 120°C, 10Pa, and reflux ratio 4 to obtain the bisdifluorophosphate product with a yield of 91.9% and a purity of 99.5%, and the bisdifluorophosphate is dehydrated. save.

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Abstract

The present application provides a preparation method for lithium difluorophosphate, and belongs to the technical field of lithium battery additive preparation. The preparation method for lithium difluorophosphate comprises the following steps: 1) respectively introducing a mixed solution of ethylene glycol and a catalyst, i.e. p-toluenesulfonic acid, and phosphoric acid into a micro-channel reactor for reaction, so as to obtain a diphosphate-containing mixture; 2) rectifying and purifying the diphosphate-containing mixture to obtain a diphosphate; 3) mixing an activated anhydrous fluorinating agent, antimony pentafluoride and an anhydrous organic solvent, adding the diphosphate dropwise, and performing a reaction after the addition is finished, so as to obtain bis-difluorophosphate; and 4) adding the bis-difluorophosphate dropwise to a mixed solution of a lithium source and anhydrous glycol dimethyl ether, and performing a reaction after the addition is finished, so as to obtain lithium difluorophosphate. The preparation method for lithium difluorophosphate provided in the present application is efficient, green and safe; the reaction raw materials have a low cost and are easily available; and the prepared product has a high purity and a high yield.

Description

二氟磷酸锂的制备方法Preparation method of lithium difluorophosphate
本申请要求在2022年12月26日提交中国专利局、申请号为202211691050.X、申请名称为“一种二氟磷酸锂的制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims priority to a Chinese patent application filed with the China Patent Office on December 26, 2022, with application number 202211691050.X and application title "A method for preparing lithium difluorophosphate", the entire content of which is incorporated by reference in this application.
技术领域Technical field
本申请属于锂电池添加剂制备技术领域，尤其涉及一种二氟磷酸锂的制备方法。The present application belongs to the technical field of lithium battery additive preparation, and particularly relates to a preparation method of lithium difluorophosphate.
背景技术Background technique
经实验表明少量二氟磷酸锂即可促进石墨负极固体电解质相界面(SEI)的形成，成膜效果明显优于碳酸亚乙烯酯，同时，单独添加二氟磷酸锂时，SEI膜中由于二氟磷酸锂的分解产生的高电阻物质氟化锂含量过高，从而影响电池高倍率下放电性能，因此当与碳酸亚乙烯酯共同使用时性能最好。Experiments have shown that a small amount of lithium difluorophosphate can promote the formation of the solid electrolyte interface (SEI) of the graphite anode, and the film-forming effect is significantly better than that of vinylene carbonate. At the same time, when lithium difluorophosphate is added alone, the SEI film due to difluoride The high-resistance substance lithium fluoride produced by the decomposition of lithium phosphate contains too much content, which affects the battery's discharge performance at high rates. Therefore, it performs best when used together with vinylene carbonate.
锂盐类添加剂的合成通常由六氟磷酸锂作为前端物料进行制备，尤其是二氟磷酸锂的合成由六氟磷酸锂与碳酸锂或六氟磷酸锂与硅氧烷反应生成。但由于六氟磷酸锂的价格较高，所以造成成本居高不下。目前二氟磷酸锂合成新工艺的发展引起了业界的广泛关注，工艺路线也在有意的避开六氟磷酸锂这种高价格的锂源。目前有利用二氟磷酸与锂源直接发生反应来制备二氟磷酸锂，但二氟磷酸本身也难以购买，目前量产二氟磷酸的企业几乎没有，并且二氟磷酸的制造工艺极其复杂，产率及纯度均较低，这种工艺路线并不能够很好的进行工业化放大。The synthesis of lithium salt additives is usually prepared by using lithium hexafluorophosphate as the front-end material. In particular, the synthesis of lithium difluorophosphate is generated by the reaction of lithium hexafluorophosphate and lithium carbonate or lithium hexafluorophosphate and siloxane. However, due to the high price of lithium hexafluorophosphate, the cost remains high. At present, the development of a new synthesis process for lithium difluorophosphate has attracted widespread attention in the industry, and the process route is also deliberately avoiding high-priced lithium sources such as lithium hexafluorophosphate. Currently, lithium difluorophosphoric acid is prepared by directly reacting difluorophosphoric acid with a lithium source. However, difluorophosphoric acid itself is difficult to purchase. Currently, there are few companies that mass-produce difluorophosphoric acid, and the manufacturing process of difluorophosphoric acid is extremely complicated. The efficiency and purity are both low, and this process route is not suitable for industrial scale-up.
专利CN114604844A先将三氯氧磷和一元醇进行酯化反应得到二氯磷酸酯；再将二氯磷酸酯与氟化试剂进行氟化得到二氟磷酸酯；最后再利用二氟 磷酸酯与锂化试剂进行锂化反应制得二氟磷酸锂。但三氯氧磷存在强腐蚀性和挥发性，比较危险，同时三氯氧磷的活性极强，得到副产物的可能性非常大，放大生产存在一定的不可控风险。利用氟化钾进行氟化，存在引入杂质钾离子的风险，而且该方法中反应耗时较长。Patent CN114604844A first esterifies phosphorus oxychloride and a monohydric alcohol to obtain dichlorophosphate; then fluorinates dichlorophosphate with a fluorinating reagent to obtain difluorophosphate; and finally utilizes difluorophosphate Lithium difluorophosphate is prepared by lithiation reaction between phosphate ester and lithiation reagent. However, phosphorus oxychloride is highly corrosive and volatile, which makes it relatively dangerous. At the same time, phosphorus oxychloride is extremely active, and the possibility of obtaining by-products is very high. There are certain uncontrollable risks in scaling up production. Using potassium fluoride for fluorination involves the risk of introducing impurity potassium ions, and the reaction in this method takes a long time.
发明内容Contents of the invention
针对现有技术中的至少一个不足之处，本申请提供了一种二氟磷酸锂的制备方法，包括如下步骤：In view of at least one shortcoming in the prior art, this application provides a preparation method of lithium difluorophosphate, which includes the following steps:
1)将乙二醇和催化剂对甲苯磺酸的混合液，以及磷酸分别通入微通道反应器内进行反应，得到含二磷酸酯的混合物；1) Pass the mixture of ethylene glycol, catalyst p-toluenesulfonic acid, and phosphoric acid into the microchannel reactor for reaction to obtain a mixture containing diphosphate;
2)将含二磷酸酯的混合物进行精馏提纯，得到二磷酸酯；2) Distillate and purify the mixture containing diphosphate to obtain diphosphate;
3)将活化后的无水氟化剂、五氟化锑和无水有机溶剂混合，滴加二磷酸酯，滴加完成后进行反应，得到双二氟磷酸酯；3) Mix the activated anhydrous fluorinating agent, antimony pentafluoride and anhydrous organic solvent, add the diphosphate ester dropwise, and react after the addition is completed to obtain bisdifluorophosphate;
4)在锂源和无水乙二醇二甲醚的混合液中滴加双二氟磷酸酯，滴加完成后进行反应，得到二氟磷酸锂。4) Add bisdifluorophosphate dropwise to the mixture of lithium source and anhydrous ethylene glycol dimethyl ether, and react after completion of the dropwise addition to obtain lithium difluorophosphate.
在本申请的一些实施例中，步骤1)中所述乙二醇与催化剂对甲苯磺酸的摩尔质量比为1mol:0.05g～0.1g；所述乙二醇与磷酸的摩尔比为1:2.0～2.5。In some embodiments of the present application, the molar mass ratio of ethylene glycol and the catalyst p-toluenesulfonic acid in step 1) is 1 mol:0.05g~0.1g; the molar ratio of ethylene glycol and phosphoric acid is 1: 2.0～2.5.
在本申请的一些实施例中，步骤1)中乙二醇和催化剂对甲苯磺酸的混合液进料速度为30～40ml/min，磷酸的进料速度为70～100ml/min；在微通道反应器内进行反应时，反应的温度为40～50℃。In some embodiments of the present application, the feed rate of the mixed solution of ethylene glycol and the catalyst p-toluenesulfonic acid in step 1) is 30-40ml/min, and the feed rate of phosphoric acid is 70-100ml/min; in the microchannel reaction When the reaction is carried out in the vessel, the reaction temperature is 40 to 50°C.
在本申请的一些实施例中，步骤2)中精馏提纯时的温度为90～120℃，真空度为30～100Pa，回流比为4～6。In some embodiments of the present application, the temperature during distillation and purification in step 2) is 90-120°C, the vacuum degree is 30-100 Pa, and the reflux ratio is 4-6.
在本申请的一些实施例中，步骤3)中所述无水氟化剂为无水氟化铵和/或无水氟化氢铵；所述无水氟化剂的活化方法为将无水氟化剂进行球磨、过 筛；所述球磨的转速为500～800rpm；所述过筛用筛网孔径为200～500目。In some embodiments of the present application, the anhydrous fluorinating agent in step 3) is anhydrous ammonium fluoride and/or anhydrous ammonium bifluoride; the activation method of the anhydrous fluorinating agent is anhydrous fluorination The agent is ball milled and passed Sieve; the rotation speed of the ball mill is 500-800 rpm; the aperture of the sieve used for screening is 200-500 mesh.
在本申请的一些实施例中，步骤3)中所述活化后的无水氟化剂与二磷酸酯的摩尔比为4.5～5.0：1；所述二磷酸酯与五氟化锑的摩尔质量比为1mol：0.03～0.08g；所述无水有机溶剂为无水四氢呋喃、无水乙腈、无水N，N-二甲基甲酰胺中的一种，无水有机溶剂的添加量为每摩尔二磷酸酯添加1L～2L无水有机溶剂。In some embodiments of the present application, the molar ratio of the activated anhydrous fluorinating agent to the diphosphate in step 3) is 4.5-5.0:1; the molar mass of the diphosphate and antimony pentafluoride The ratio is 1 mol: 0.03 ~ 0.08g; the anhydrous organic solvent is one of anhydrous tetrahydrofuran, anhydrous acetonitrile, and anhydrous N, N-dimethylformamide, and the added amount of the anhydrous organic solvent is per mole Add 1L to 2L anhydrous organic solvent to the diphosphate.
在本申请的一些实施例中，步骤3)中二磷酸酯的滴加速度为每摩尔液体滴加0.5～2h，所述反应的温度为85～100℃，滴加完成后进行反应的时间为3～5h。In some embodiments of the present application, the dropping rate of the diphosphate in step 3) is 0.5 to 2 hours per mole of liquid, the temperature of the reaction is 85 to 100°C, and the reaction time after the dropwise addition is completed is 3 ~5h.
在本申请的一些实施例中，步骤4)中所述锂源为氢氧化锂，所述双二氟磷酸酯与锂源的摩尔比为1:2.1～3；所述双二氟磷酸酯与无水乙二醇二甲醚的摩尔体积比为1mol:2.5～3L。In some embodiments of the present application, the lithium source in step 4) is lithium hydroxide, and the molar ratio of the bisdifluorophosphate to the lithium source is 1:2.1~3; the bisdifluorophosphate and The molar volume ratio of anhydrous ethylene glycol dimethyl ether is 1mol:2.5~3L.
在本申请的一些实施例中，步骤4)中，所述双二氟磷酸酯的滴加速度为每摩尔滴加2～3h；所述反应的温度为50～70℃，滴加完成后进行反应的时间为1～2h。In some embodiments of the present application, in step 4), the dropping rate of the bisdifluorophosphate is 2 to 3 hours per mole; the reaction temperature is 50 to 70°C, and the reaction is carried out after the dropwise addition is completed The time is 1~2h.
在本申请的一些实施例中，步骤4)中反应结束后，还包括纯化和干燥；所述纯化的方式为将反应产物依次进行过滤、旋蒸、重结晶和抽滤；所述旋蒸的条件为100～120℃，真空度-0.08～-0.1MPa；所述干燥的温度为80～120℃，真空度为30～80Pa。In some embodiments of the present application, after the reaction in step 4) is completed, purification and drying are also included; the purification method is to sequentially filter, rotary evaporate, recrystallize and suction filtrate the reaction product; the rotary evaporated The conditions are 100~120°C and the vacuum degree is -0.08~-0.1MPa; the drying temperature is 80~120°C and the vacuum degree is 30~80Pa.
与现有技术相比，本申请的优点和积极效果在于：Compared with the existing technology, the advantages and positive effects of this application are:
本申请至少一个实施例所提供的二氟磷酸锂的制备方法，首先利用乙二醇与磷酸在酯化反应催化剂的作用下，在微通道反应器内进行酯化反应，生成二磷酸酯，随后将二磷酸酯，利用高活性氟化剂进行氟化，氟化成为双二氟磷酸酯。最后，将双二氟磷酸酯与锂源进行反应，得到高纯度的二氟磷酸 锂产品。本申请所采用的原料乙二醇与磷酸、氟化铵及氟化氢铵均为安全系数较高，且均是成本低的大宗产品。同时采用这些原料不会引入杂质金属离子，为产物的纯度进一步提供了保障。整个反应过程无强污染废气及强污染液体产生。利用微通道反应器及酯类催化剂的帮助下进行酯化反应，可以很好的加速反应进行。采用双二氟磷酸酯与锂源进行反应，生产效率更高。The preparation method of lithium difluorophosphate provided in at least one embodiment of the present application first uses ethylene glycol and phosphoric acid to perform an esterification reaction in a microchannel reactor under the action of an esterification reaction catalyst to generate a diphosphate ester, and then The diphosphate is fluorinated using a highly active fluorinating agent to become bisdifluorophosphate. Finally, the bisdifluorophosphate is reacted with a lithium source to obtain high-purity difluorophosphate Lithium Products. The raw materials ethylene glycol, phosphoric acid, ammonium fluoride and ammonium bifluoride used in this application are all bulk products with high safety factor and low cost. At the same time, using these raw materials will not introduce impurity metal ions, further ensuring the purity of the product. There is no strong polluting waste gas or strong polluting liquid produced during the entire reaction process. Using microchannel reactors and ester catalysts to carry out esterification reactions can accelerate the reaction very well. Using bisdifluorophosphate to react with lithium source, the production efficiency is higher.
(2)本申请至少一个实施例所提供的二氟磷酸锂的制备方法，高效、绿色、安全，反应原料成本低，易获取，且制备得到的产品纯度高、收率高。(2) The preparation method of lithium difluorophosphate provided in at least one embodiment of the present application is efficient, green, and safe. The reaction raw materials are low in cost and easy to obtain, and the prepared product has high purity and high yield.
具体实施方式Detailed ways
下面将对本申请实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。The technical solutions in the embodiments of the present application will be clearly and completely described below. Obviously, the described embodiments are only some of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in this application, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of this application.
本申请实施例提供了一种二氟磷酸锂的制备方法，包括如下步骤：The embodiments of the present application provide a method for preparing lithium difluorophosphate, which includes the following steps:
1)将乙二醇和催化剂对甲苯磺酸的混合液，以及磷酸分别通入微通道反应器内进行反应，得到含二磷酸酯的混合物；1) Pass the mixture of ethylene glycol, catalyst p-toluenesulfonic acid, and phosphoric acid into the microchannel reactor for reaction to obtain a mixture containing diphosphate;
2)将含二磷酸酯的混合物进行精馏提纯，得到二磷酸酯；2) Distillate and purify the mixture containing diphosphate to obtain diphosphate;
3)将活化后的无水氟化剂、五氟化锑和无水有机溶剂混合，滴加二磷酸酯，滴加完成后进行反应，得到双二氟磷酸酯；3) Mix the activated anhydrous fluorinating agent, antimony pentafluoride and anhydrous organic solvent, add the diphosphate ester dropwise, and react after the addition is completed to obtain bisdifluorophosphate;
4)在锂源和无水乙二醇二甲醚的混合液中滴加双二氟磷酸酯，滴加完成后进行反应，得到二氟磷酸锂。4) Add bisdifluorophosphate dropwise to the mixture of lithium source and anhydrous ethylene glycol dimethyl ether, and react after completion of the dropwise addition to obtain lithium difluorophosphate.
以上实施例将乙二醇和催化剂对甲苯磺酸的混合液，以及磷酸分别通入微通道反应器内进行反应，得到含二磷酸酯的混合物。In the above embodiment, a mixture of ethylene glycol, catalyst p-toluenesulfonic acid, and phosphoric acid were separately introduced into a microchannel reactor for reaction to obtain a mixture containing diphosphate.
在一些实施例中，所述乙二醇与催化剂对甲苯磺酸的摩尔质量比为 1mol:0.05g～0.1g；所述乙二醇与磷酸的摩尔比为1:2.0～2.5。In some embodiments, the molar mass ratio of the ethylene glycol to the catalyst p-toluenesulfonic acid is 1mol:0.05g～0.1g; the molar ratio of ethylene glycol and phosphoric acid is 1:2.0～2.5.
在一些实施例中，先采用氮气对反应器管道进行吹扫，吹扫完毕后先升温至反应温度后再通入物料。通过这样的操作以便排净管道内的空气及杂质，避免对反应造成影响。In some embodiments, nitrogen gas is first used to purge the reactor pipeline. After the purging is completed, the temperature is raised to the reaction temperature before the materials are introduced. This operation is used to drain the air and impurities in the pipeline to avoid affecting the reaction.
在一些实施例中，所述反应的温度为40～50℃。In some embodiments, the reaction temperature is 40-50°C.
在一些实施例中，所述乙二醇和催化剂对甲苯磺酸的混合液进料速度为30～40ml/min，磷酸的进料速度为70～100ml/min。通过控制混合液与磷酸的进料速度可以控制反应内部整体的PH以及物相的富集程度，进而可以使整个反应不会随着加料的变化，从而避免导致整个体系内部某种物质出现浓度过高及过低的情况。In some embodiments, the feed rate of the mixed liquid of ethylene glycol and catalyst p-toluenesulfonic acid is 30-40 ml/min, and the feed rate of phosphoric acid is 70-100 ml/min. By controlling the feed rate of the mixed liquid and phosphoric acid, the overall pH and the enrichment degree of the material phase within the reaction can be controlled, so that the entire reaction will not change with the addition of materials, thereby avoiding excessive concentration of certain substances within the entire system. High and too low conditions.
本申请对所述微通道反应器的类型没有特殊限定，采用本领域常规市售产品即可。在一些实施例中采用康宁G1微通道反应器。This application has no special limitations on the type of microchannel reactor, and conventional commercially available products in this field can be used. Corning G1 microchannel reactors are used in some embodiments.
得到含二磷酸酯的混合物后，本申请将所述含二磷酸酯的混合物进行精馏提纯，得到二磷酸酯。在一些实施例中，所述精馏提纯的温度为90～120℃，真空度为30～100Pa，回流比为4～6。在一些实施例中，得到二磷酸酯后，在未使用时，将其在密封条件下放置。After obtaining the diphosphate-containing mixture, the present application performs distillation and purification on the diphosphate-containing mixture to obtain the diphosphate. In some embodiments, the temperature of the distillation and purification is 90-120°C, the vacuum degree is 30-100 Pa, and the reflux ratio is 4-6. In some embodiments, after obtaining the diphosphate, it is placed under sealed conditions when not in use.
本申请将活化后的无水氟化剂、五氟化锑和无水有机溶剂混合，滴加二磷酸酯，滴加完成后进行反应，得到双二氟磷酸酯。在一些实施例中，所述无水氟化剂为无水氟化铵和/或无水氟化氢铵；所述无水氟化剂的活化方法为将无水氟化剂进行球磨、过筛；所述球磨的转速为500～800rpm；所述过筛用筛网孔径为200～500目。将无水氟化剂进行球磨破碎，可激发氟化剂的反应活性，降低反应温度，使得反应避免在较高温度下才会引发。In this application, the activated anhydrous fluorinating agent, antimony pentafluoride and anhydrous organic solvent are mixed, the diphosphate is added dropwise, and the reaction is carried out after the dropwise addition is completed to obtain the bisdifluorophosphate. In some embodiments, the anhydrous fluorinating agent is anhydrous ammonium fluoride and/or anhydrous ammonium bifluoride; the activation method of the anhydrous fluorinating agent is ball milling and sieving the anhydrous fluorinating agent; The rotation speed of the ball mill is 500-800 rpm; the aperture of the sieving mesh is 200-500 mesh. Ball milling the anhydrous fluorinating agent can stimulate the reactivity of the fluorinating agent, lower the reaction temperature, and prevent the reaction from initiating at higher temperatures.
在一些实施例中，二磷酸酯的滴加速度为每摩尔液体滴加0.5～2h，所述 反应的温度为85～100℃，滴加完成后进行反应的时间为3～5h。通过采用滴加的方式可以使得反应物更好的进行分散，配合反应器的搅拌，使得酯类可以和过量的无水氟化剂进行充分的接触，进而使得氟化效率更加的充分，确保尽可能多的酯类被氟化完全。In some embodiments, the dropping rate of the diphosphate is 0.5 to 2 hours per mole of liquid. The reaction temperature is 85 to 100°C, and the reaction time after the dropwise addition is completed is 3 to 5 hours. By using dropwise addition, the reactants can be better dispersed, and with the stirring of the reactor, the esters can fully contact with the excess anhydrous fluorinating agent, thereby making the fluorination efficiency more sufficient and ensuring that It is possible that many esters are fully fluorinated.
在一些实施例中，所述活化后的无水氟化剂与二磷酸酯的摩尔比为4.5～5.0：1；所述二磷酸酯与五氟化锑的摩尔质量比为1mol：0.03～0.08g；所述无水有机溶剂为无水四氢呋喃、无水乙腈、无水N，N-二甲基甲酰胺中的一种，无水有机溶剂的添加量为每摩尔二磷酸酯添加1L～2L无水有机溶剂。In some embodiments, the molar ratio of the activated anhydrous fluorinating agent to the diphosphate is 4.5-5.0:1; the molar mass ratio of the diphosphate to antimony pentafluoride is 1 mol: 0.03-0.08 g; the anhydrous organic solvent is one of anhydrous tetrahydrofuran, anhydrous acetonitrile, and anhydrous N, N-dimethylformamide. The amount of the anhydrous organic solvent added is 1L to 2L per mole of diphosphate. Anhydrous organic solvent.
在上述实施例中，采用上述无水有机溶剂可以彻底排除水分对于反应的影响，例如某些磷酸酯遇水后，可能会在其他物质的催化下发生分解，并且如果氟化剂接触水后，由于高温的作用，氟化剂会更加容易发生分解，变为氢氟酸或者氨气等有毒有害物质，并且上述无水有机溶剂均为沸点不高的物质，可以实现温度保持控制在沸腾温度以下，防止物质过热分解。In the above embodiments, the use of the above-mentioned anhydrous organic solvent can completely eliminate the influence of moisture on the reaction. For example, when certain phosphate esters come into contact with water, they may decompose under the catalysis of other substances, and if the fluorinating agent comes into contact with water, Due to the effect of high temperature, the fluorinating agent will be more likely to decompose and turn into toxic and harmful substances such as hydrofluoric acid or ammonia. Moreover, the above-mentioned anhydrous organic solvents are substances with low boiling points, so the temperature can be kept below the boiling temperature. , to prevent overheating and decomposition of substances.
在一些实施例中，所述双二氟磷酸酯为二氟磷酸酐类物质，在专利JP2008287965中公开了二氟磷酸酐类物质。但该专利中采用的二氟磷酸酐成本较高，本申请中采用乙二醇和磷酸为原料，制备成双二氟磷酸酯，原料成本低，且反应简单，更适合工业化生产。In some embodiments, the bisdifluorophosphate is a difluorophosphoric anhydride substance, which is disclosed in patent JP2008287965. However, the cost of difluorophosphoric anhydride used in this patent is relatively high. In this application, ethylene glycol and phosphoric acid are used as raw materials to prepare bisdifluorophosphoric acid ester. The raw material cost is low and the reaction is simple, making it more suitable for industrial production.
得到双二氟磷酸酯后，本申请在锂源和无水乙二醇二甲醚的混合液中滴加双二氟磷酸酯，滴加完成后进行反应，得到二氟磷酸锂。在一些实施例中，将得到的双二氟磷酸酯进行精馏提纯后再进行反应。After obtaining bisdifluorophosphate, this application adds bisdifluorophosphate dropwise to the mixture of lithium source and anhydrous ethylene glycol dimethyl ether. After the dropwise addition is completed, the reaction proceeds to obtain lithium difluorophosphate. In some embodiments, the obtained bisdifluorophosphate is subjected to distillation and purification before reaction.
在一些实施例中，所述精馏提纯的温度为120～150℃，真空度为10～30Pa，回流比为4～6。In some embodiments, the temperature of the distillation and purification is 120-150°C, the vacuum degree is 10-30 Pa, and the reflux ratio is 4-6.
在一些实施例中，所述双二氟磷酸酯的滴加速度为每摩尔滴加2～3h；所 述反应的温度为50～70℃，滴加完成后进行反应的时间为1～2h。In some embodiments, the dropping rate of the bisdifluorophosphate is 2 to 3 hours per mole; so The temperature of the reaction is 50 to 70°C, and the reaction time after the dropwise addition is completed is 1 to 2 hours.
在一些实施例中，所述锂源为氢氧化锂；所述双二氟磷酸酯与锂源的摩尔比为1:2.1～3；所述双二氟磷酸酯与无水乙二醇二甲醚的摩尔体积比为1mol:2.5～3L。In some embodiments, the lithium source is lithium hydroxide; the molar ratio of the bisdifluorophosphate to the lithium source is 1:2.1~3; the bisdifluorophosphate and anhydrous ethylene glycol dimethyl The molar volume ratio of ether is 1mol:2.5~3L.
现有技术中有直接采用二卤素磷酸酯与锂源反应进行合成二氟磷酸锂，但二卤素磷酸酯本身就不是大宗产品，难以购买。在本申请实施例中，采用二磷酸酯氟化制备双二氟磷酸酯，易制备，且双二氟磷酸酯较二氟磷酸酯生产效率高，这是因为双二氟磷酸酯由于双端具备官能团，反应的活性较二氟磷酸酯的活性要更高一些，并且因为分子结构较大，可以能够很好的发生断键，促进反应的进一步形成。并且最终反应生成的醇类物质，经过精馏提纯还可以重复利用于下一次的反应中，实现反应物的循环利用，节约生产成本。同时，双二氟磷酸酯由于采用的制备原料更加安全与低成本，因此较二氟磷酸酯具有更多的优势。In the prior art, lithium difluorophosphate is directly synthesized by reacting dihalogen phosphate ester with a lithium source, but dihalogen phosphate itself is not a bulk product and is difficult to purchase. In the embodiment of the present application, bisdifluorophosphate is prepared by fluorination of diphosphate, which is easy to prepare, and the production efficiency of bisdifluorophosphate is higher than that of difluorophosphate. This is because bisdifluorophosphate has double-terminal properties. The reaction activity of functional groups is higher than that of difluorophosphate, and because of its larger molecular structure, it can break bonds well and promote the further formation of the reaction. And the alcohols generated by the final reaction can be reused in the next reaction after distillation and purification, realizing the recycling of reactants and saving production costs. At the same time, bisdifluorophosphate has more advantages than difluorophosphate because the raw materials used for preparation are safer and lower cost.
在一些实施例中，反应结束后，还包括纯化和干燥。In some embodiments, after the reaction is completed, purification and drying are also included.
在一些实施例中，所述纯化的方式为将反应产物依次进行过滤、旋蒸、重结晶和抽滤。In some embodiments, the purification method includes filtering, rotary evaporation, recrystallization and suction filtration of the reaction product in sequence.
在一些实施例中，所述旋蒸的条件为100～120℃，真空度为-0.08～-0.1MPa。In some embodiments, the rotary evaporation conditions are 100 to 120°C, and the vacuum degree is -0.08 to -0.1MPa.
在一些实施例中，所述重结晶用溶剂为二氯甲烷和/或正己烷；所述重结晶用溶剂的添加量为每摩尔双二氟磷酸酯添加500-800ml溶剂。In some embodiments, the solvent for recrystallization is methylene chloride and/or n-hexane; the added amount of the solvent for recrystallization is 500-800 ml of solvent per mole of bisdifluorophosphate.
在一些实施例中，所述干燥的温度为80～120℃，真空度为30～80Pa。In some embodiments, the drying temperature is 80-120°C, and the vacuum degree is 30-80 Pa.
在本申请实施例中，制备二氟磷酸锂的反应方程式如下所示：
In the embodiment of this application, the reaction equation for preparing lithium difluorophosphate is as follows:
为了进一步说明本申请，下面结合具体实施例对本申请提供的技术方案进行详细地描述，但不能将它们理解为对本申请保护范围的限定。In order to further illustrate the present application, the technical solutions provided by the present application are described in detail below in conjunction with specific examples, but they should not be understood as limiting the protection scope of the present application.
实施例1Example 1
将9.2mol乙二醇与0.6g酯化催化剂对甲苯磺酸(cas 6192-52-5)于反应瓶内常温进行机械搅拌预混，得到乙二醇和催化剂对甲苯磺酸的混合液。将反应器内用氮气进行吹扫，随后开启升温，反应温度控制在45℃，待反应器达到反应温度后，将乙二醇和催化剂对甲苯磺酸的混合液与18.0mol磷酸溶液分别通过柱塞泵注入微通道反应器内进行反应(其中混合液从内测进料，加料速度为30ml/min；磷酸从外侧进料，加料速度为80ml/min)，得到含二磷酸酯、磷酸酯、水及其他杂质的反应液。将反应液进行精馏提纯(精馏条件为110℃，真空度30Pa，回流比选择6)，得到二磷酸酯收率89.4％，纯度99.1％， 二磷酸酯密封放置备用。9.2 mol of ethylene glycol and 0.6 g of the esterification catalyst p-toluenesulfonic acid (cas 6192-52-5) were mechanically stirred and premixed at room temperature in the reaction bottle to obtain a mixed solution of ethylene glycol and the catalyst p-toluenesulfonic acid. The reactor was purged with nitrogen, and then the temperature was turned on. The reaction temperature was controlled at 45°C. After the reactor reached the reaction temperature, the mixture of ethylene glycol and catalyst p-toluenesulfonic acid and 18.0 mol of phosphoric acid solution were passed through the plunger respectively. The pump is injected into the microchannel reactor for reaction (the mixed liquid is fed from the inside at a feeding rate of 30 ml/min; phosphoric acid is fed from the outside at a feeding rate of 80 ml/min) to obtain a mixture containing diphosphate, phosphate, and water. and other impurities in the reaction solution. The reaction liquid was subjected to distillation and purification (distillation conditions were 110°C, vacuum degree 30Pa, reflux ratio selected 6) to obtain a diphosphate yield of 89.4% and a purity of 99.1%. Seal the diphosphate and set aside.
取11mol无水氟化铵加入到球磨机中，于500rpm的转速下进行球磨，过300目不锈钢筛网进行筛分，取筛下物活化无水氟化铵10.5mol，将其加入到反应釜内，随后加入无水乙腈3.75L进行保护，升至85℃后，加入0.16g催化剂五氟化锑。随后，将2.25mol二磷酸酯进行滴加，2h滴加完成后，反应3h。待反应产物冷却后，将其在120℃，10Pa，回流比4的条件下进行精馏，得到双二氟磷酸酯产品收率92.8％，纯度99.4％，并将双二氟磷酸酯进行绝水保存。Take 11 mol of anhydrous ammonium fluoride and add it to the ball mill, conduct ball milling at 500 rpm, sieve through a 300 mesh stainless steel screen, take 10.5 mol of activated anhydrous ammonium fluoride under the sieve, and add it to the reaction kettle , then add 3.75L of anhydrous acetonitrile for protection. After rising to 85°C, add 0.16g of catalyst antimony pentafluoride. Subsequently, 2.25 mol of diphosphate was added dropwise. After the dropwise addition was completed in 2 hours, the reaction was continued for 3 hours. After the reaction product is cooled, it is rectified at 120°C, 10 Pa, and reflux ratio 4 to obtain the bisdifluorophosphate product with a yield of 92.8% and a purity of 99.4%. The bisdifluorophosphate is dehydrated. save.
取2.3mol氢氧化锂溶解于2.8L无水乙二醇二甲醚内，加入反应釜中，待温度升至60℃后，滴加1mol双二氟磷酸酯，2.5h滴加完成后，反应1h，将产物利用微孔滤膜(0.45μm，PTFE材质)过滤，滤液取出进行旋蒸(旋蒸条件为100℃，真空度为-0.1MPa)，剩余约50ml溶液时，停止旋蒸，加入800ml重结晶溶剂正己烷，将混合液抽滤，取滤饼即为二氟磷酸锂粗品。将粗品于真空烘箱内烘干(干燥条件为100℃，真空度为30Pa)，最终得到纯净的二氟磷酸锂产品，产品纯度99.93％，产品综合收率82.54％，水分为8.4ppm。Dissolve 2.3 mol of lithium hydroxide in 2.8 L of anhydrous ethylene glycol dimethyl ether and add it to the reaction kettle. After the temperature rises to 60°C, add 1 mol of bisdifluorophosphate dropwise. After the dropwise addition is completed in 2.5 hours, the reaction 1h, filter the product using a microporous filter membrane (0.45μm, PTFE material), take out the filtrate and perform rotary evaporation (rotary evaporation conditions are 100°C, vacuum degree is -0.1MPa). When about 50ml of solution remains, stop rotary evaporation and add Use 800 ml of recrystallization solvent n-hexane, filter the mixture with suction, and take the filter cake to obtain crude lithium difluorophosphate. The crude product was dried in a vacuum oven (drying conditions were 100°C, vacuum degree was 30Pa), and finally a pure lithium difluorophosphate product was obtained, with a product purity of 99.93%, a comprehensive product yield of 82.54%, and a moisture content of 8.4ppm.
其中产品指标测试方法如下：The product index testing methods are as follows:
(1)纯度测试：采用离子色谱的外标法来进行纯度测试。(1) Purity test: Use the external standard method of ion chromatography to conduct the purity test.
(2)用卡式炉将二氟磷酸锂样品加热至一定温度，用干燥空气将蒸发的水汽吹入反应杯里的卡尔费休试剂中，用库伦法测定。(2) Use a cassette furnace to heat the lithium difluorophosphate sample to a certain temperature, use dry air to blow the evaporated water vapor into the Karl Fischer reagent in the reaction cup, and measure it using the Coulomb method.
(3)样品按照乙二醇的摩尔量进行计算，所得样品的质量除以理论生成量既得产率。(3) The sample is calculated according to the molar amount of ethylene glycol, and the mass of the sample obtained is divided by the theoretical production amount to obtain the yield.
(4)产品综合收率为三步骤相乘，最终产物收率。(4) The comprehensive yield of the product is the final product yield multiplied by the three steps.
实施例2Example 2
将9.2mol乙二醇与0.7g酯化催化剂对甲苯磺酸(cas 6192-52-5)于反应 瓶内常温进行机械搅拌预混，得到乙二醇和催化剂对甲苯磺酸的混合液。将反应器内用氮气进行吹扫，随后开启升温，反应温度控制在50℃，待反应器达到反应温度后，将乙二醇和催化剂对甲苯磺酸的混合液与20mol磷酸溶液分别通过柱塞泵注入微通道反应器内进行反应(其中混合液从内测进料，加料速度为40ml/min；磷酸从外侧进料，加料速度为100ml/min)，得到含二磷酸酯、磷酸酯、水及其他杂质的反应液。将反应液进行精馏提纯(精馏条件为110℃，真空度30Pa，回流比选择5)产品收率91.4％，纯度99.3％，得到二磷酸酯，二磷酸酯密封放置备用。React 9.2mol ethylene glycol with 0.7g esterification catalyst p-toluenesulfonic acid (cas 6192-52-5) Mechanically stir and premix at room temperature in the bottle to obtain a mixed solution of ethylene glycol and catalyst p-toluenesulfonic acid. The reactor was purged with nitrogen, and then the temperature was turned on. The reaction temperature was controlled at 50°C. After the reactor reached the reaction temperature, the mixture of ethylene glycol and catalyst p-toluenesulfonic acid and 20 mol of phosphoric acid solution were passed through the plunger pump respectively. Inject into the microchannel reactor for reaction (the mixed liquid is fed from the inside, the feeding speed is 40ml/min; the phosphoric acid is fed from the outside, the feeding speed is 100ml/min), and the mixture containing diphosphate, phosphate, water and Reaction solution containing other impurities. The reaction solution was subjected to distillation and purification (distillation conditions were 110°C, vacuum degree 30Pa, reflux ratio selected 5) with a product yield of 91.4% and a purity of 99.3% to obtain a diphosphate, which was sealed and placed for later use.
取12mol无水氟化铵加入到球磨机中，于600rpm的转速下进行球磨，过200目不锈钢筛网进行筛分，取筛下物活化无水氟化铵11.25mol，将其加入到反应釜内，随后加入无水四氢呋喃3L进行保护，升至85℃后，加入0.1125g催化剂五氟化锑。随后，将2.25mol二磷酸酯进行滴加，2h滴加完成后，反应3h。待反应产物冷却后，将其在150℃，30Pa，回流比4的条件下进行精馏，得到双二氟磷酸酯产品收率94.1％，纯度99.2％，并将双二氟磷酸酯进行绝水保存。Take 12 mol of anhydrous ammonium fluoride and add it to the ball mill, conduct ball milling at a speed of 600 rpm, sieve through a 200 mesh stainless steel screen, take 11.25 mol of activated anhydrous ammonium fluoride under the sieve, and add it to the reaction kettle , then add 3L of anhydrous tetrahydrofuran for protection, and after rising to 85°C, add 0.1125g of catalyst antimony pentafluoride. Subsequently, 2.25 mol of diphosphate was added dropwise. After the dropwise addition was completed in 2 hours, the reaction was continued for 3 hours. After the reaction product is cooled, it is rectified at 150°C, 30 Pa, and reflux ratio 4 to obtain the bisdifluorophosphate product with a yield of 94.1% and a purity of 99.2%, and the bisdifluorophosphate is dehydrated. save.
取2.5mol氢氧化锂溶解于3L无水乙二醇二甲醚内，加入反应釜中，待温度升至60℃后，滴加1mol双二氟磷酸酯，2.5h滴加完成后，反应2h，将产物利用微孔滤膜(0.45μm，PTFE材质)过滤，滤液取出进行旋蒸(旋蒸条件为100℃，真空度为-0.1MPa)，剩余约50ml溶液时，停止旋蒸，加入700ml重结晶溶剂二氯甲烷，将混合液抽滤，取滤饼即为二氟磷酸锂粗品。将粗品于真空烘箱内烘干(干燥条件为100℃，真空度为50Pa)，最终得到纯净的二氟磷酸锂产品，产品纯度99.95％，产品综合收率81.8％，水分为7.4ppm。Dissolve 2.5 mol of lithium hydroxide in 3 L of anhydrous glycol dimethyl ether and add it to the reaction kettle. After the temperature rises to 60°C, add 1 mol of bisdifluorophosphate dropwise. After 2.5 hours of dripping, react for 2 hours. , filter the product using a microporous filter membrane (0.45μm, PTFE material), take out the filtrate and perform rotary evaporation (rotary evaporation conditions are 100°C, vacuum degree is -0.1MPa). When about 50ml of solution remains, stop rotary evaporation and add 700ml Recrystallize the solvent dichloromethane, filter the mixture with suction, and take the filter cake to obtain crude lithium difluorophosphate. The crude product is dried in a vacuum oven (drying conditions are 100°C, vacuum degree is 50Pa), and finally a pure lithium difluorophosphate product is obtained, with a product purity of 99.95%, a comprehensive product yield of 81.8%, and a moisture content of 7.4ppm.
实施例3 Example 3
将9.2mol乙二醇与0.9g酯化催化剂对甲苯磺酸(cas 6192-52-5)于反应瓶内常温进行机械搅拌预混，得到乙二醇和催化剂对甲苯磺酸的混合液。将反应器内用氮气进行吹扫，随后开启升温，反应温度控制在40℃，待反应器达到反应温度后，将乙二醇和催化剂对甲苯磺酸的混合液与22mol磷酸溶液分别通过柱塞泵注入微通道反应器内进行反应(其中混合液从内测进料，加料速度为35ml/min；磷酸从外侧进料，加料速度为90ml/min)，得到含二磷酸酯、磷酸酯、水及其他杂质的反应液。将反应液进行精馏提纯(精馏条件为90℃，真空度100Pa，回流比选择4)，得到二磷酸酯产品收率90.2％，纯度99.5％，二磷酸酯密封放置备用。9.2mol ethylene glycol and 0.9g esterification catalyst p-toluenesulfonic acid (cas 6192-52-5) were mechanically stirred and premixed at room temperature in the reaction bottle to obtain a mixed solution of ethylene glycol and catalyst p-toluenesulfonic acid. The reactor was purged with nitrogen, and then the temperature was turned on. The reaction temperature was controlled at 40°C. After the reactor reached the reaction temperature, the mixture of ethylene glycol and catalyst p-toluenesulfonic acid and 22 mol of phosphoric acid solution were passed through the plunger pump respectively. Inject into the microchannel reactor for reaction (the mixed liquid is fed from the inside, the feeding speed is 35ml/min; the phosphoric acid is fed from the outside, the feeding speed is 90ml/min), and the mixture containing diphosphate, phosphate, water and Reaction solution containing other impurities. The reaction solution was subjected to distillation and purification (distillation conditions were 90°C, vacuum degree 100Pa, reflux ratio selected 4) to obtain a diphosphate product with a yield of 90.2% and a purity of 99.5%. The diphosphate was sealed and placed for later use.
取12mol无水氟化氢铵加入到球磨机中，于800rpm的转速下进行球磨，过500目不锈钢筛网进行筛分，取筛下物活化无水氟化铵11.25mol，将其加入到反应釜内，随后加入无水N,N-二甲基甲酰胺2L进行保护，升至100℃后，加入0.15g催化剂五氟化锑。随后，将2.25mol二磷酸酯进行滴加，1h滴加完成后，反应5h。待反应产物冷却后，将其在120℃，10Pa，回流比4的条件下进行精馏，得到双二氟磷酸酯产品收率93.6％，纯度99.3％，并将双二氟磷酸酯进行绝水保存。Take 12 mol of anhydrous ammonium bifluoride and add it to the ball mill, conduct ball milling at 800 rpm, sieve through a 500 mesh stainless steel screen, take 11.25 mol of activated anhydrous ammonium fluoride under the sieve, and add it to the reaction kettle. Then 2L of anhydrous N,N-dimethylformamide was added for protection. After rising to 100°C, 0.15g of catalyst antimony pentafluoride was added. Subsequently, 2.25 mol of diphosphate was added dropwise. After the dropwise addition was completed in 1 hour, the reaction was continued for 5 hours. After the reaction product is cooled, it is rectified at 120°C, 10 Pa, and reflux ratio 4 to obtain the bisdifluorophosphate product with a yield of 93.6% and a purity of 99.3%. The bisdifluorophosphate is dehydrated. save.
取2.7mol氢氧化锂溶解于2.83L无水乙二醇二甲醚内，加入反应釜中，待温度升至65℃后，滴加1mol双二氟磷酸酯，2.5h滴加完成后，反应2h，将产物利用微孔滤膜(0.45μm，PTFE材质)过滤，滤液取出进行旋蒸(旋蒸条件为100℃，真空度为-0.1MPa)，剩余约50ml溶液时，停止旋蒸，加入600ml重结晶溶剂二氯甲烷，将混合液抽滤，取滤饼即为二氟磷酸锂粗品。将粗品于真空烘箱内烘干(干燥条件为100℃，真空度为50Pa)，最终得到纯净的二氟磷酸锂产品，产品纯度99.89％，产品收率82.18％，水分为7.9ppm。 Dissolve 2.7 mol of lithium hydroxide in 2.83 L of anhydrous ethylene glycol dimethyl ether and add it to the reaction kettle. After the temperature rises to 65°C, add 1 mol of bisdifluorophosphate dropwise. After the dropwise addition is completed in 2.5 hours, the reaction 2h, filter the product using a microporous filter membrane (0.45μm, PTFE material), take out the filtrate and perform rotary evaporation (rotary evaporation conditions are 100°C, vacuum degree is -0.1MPa). When about 50ml of solution remains, stop rotary evaporation and add 600ml of recrystallization solvent methylene chloride, the mixture is suction filtered, and the filter cake is taken as crude lithium difluorophosphate. The crude product was dried in a vacuum oven (drying condition: 100°C, vacuum degree: 50Pa), and finally a pure lithium difluorophosphate product was obtained, with a product purity of 99.89%, a product yield of 82.18%, and a moisture content of 7.9ppm.
对比例1Comparative example 1
与实施例1的区别在于，所用无水氟化剂并不经过活化，直接采用试剂级原料，其他操作步骤与实施例1完全相同，具体操作如下：The difference from Example 1 is that the anhydrous fluorinating agent used does not undergo activation and directly uses reagent grade raw materials. The other operating steps are exactly the same as Example 1. The specific operations are as follows:
将9.2mol乙二醇与0.6g酯化催化剂对甲苯磺酸(cas 6192-52-5)于反应瓶内常温进行机械搅拌预混，得到乙二醇和催化剂对甲苯磺酸的混合液。将反应器内用氮气进行吹扫，随后开启升温，反应温度控制在45℃，待反应器达到反应温度后，将乙二醇和催化剂对甲苯磺酸的混合液与18mol磷酸溶液分别通过柱塞泵注入微通道反应器内进行反应(其中混合液从内测进料，加料速度为30ml/min；磷酸从外侧进料，加料速度为80ml/min)，得到含二磷酸酯、磷酸酯、水及其他杂质的反应液。将反应液进行精馏提纯(精馏条件为110℃，真空度30Pa，回流比选择6)，得到二磷酸酯产品收率90.1％，纯度99.2％，二磷酸酯密封放置备用。9.2 mol of ethylene glycol and 0.6 g of esterification catalyst p-toluenesulfonic acid (cas 6192-52-5) were mechanically stirred and premixed at room temperature in the reaction bottle to obtain a mixed solution of ethylene glycol and catalyst p-toluenesulfonic acid. The reactor was purged with nitrogen, and then the temperature was turned on. The reaction temperature was controlled at 45°C. After the reactor reached the reaction temperature, the mixture of ethylene glycol and catalyst p-toluenesulfonic acid and 18 mol of phosphoric acid solution were passed through the plunger pump respectively. Inject into the microchannel reactor for reaction (the mixed liquid is fed from the inside, the feeding speed is 30ml/min; the phosphoric acid is fed from the outside, the feeding speed is 80ml/min), and the mixture containing diphosphate, phosphate, water and Reaction solution containing other impurities. The reaction solution was subjected to distillation and purification (distillation conditions were 110°C, vacuum degree 30Pa, reflux ratio selected 6) to obtain a diphosphate product with a yield of 90.1% and a purity of 99.2%. The diphosphate was sealed and placed for later use.
取11.25mol无水氟化铵将其加入到反应釜内，随后加入无水乙腈3.75L进行保护，升至85℃后，加入0.12g催化剂五氟化锑。随后，将2.25mol二磷酸酯进行滴加，2h滴加完成后，反应3h。待反应产物冷却后，将其在120℃，10Pa，回流比4的条件下进行精馏，得到双二氟磷酸酯产品收率80.4％，纯度98.6％，并将双二氟磷酸酯进行绝水保存。Take 11.25 mol of anhydrous ammonium fluoride and add it to the reaction kettle, then add 3.75L of anhydrous acetonitrile for protection. After rising to 85°C, add 0.12g of catalyst antimony pentafluoride. Subsequently, 2.25 mol of diphosphate was added dropwise. After the dropwise addition was completed in 2 hours, the reaction was continued for 3 hours. After the reaction product is cooled, it is rectified under the conditions of 120°C, 10Pa, and reflux ratio 4 to obtain the bisdifluorophosphate product with a yield of 80.4% and a purity of 98.6%, and the bisdifluorophosphate is dehydrated. save.
取2.3mol氢氧化锂溶解于2.8L无水乙二醇二甲醚内，加入反应釜中，待温度升至60℃后，滴加1mol双二氟磷酸酯，2.5h滴加完成后，反应1h，将产物利用微孔滤膜(0.45μm，PTFE材质)过滤，滤液取出进行旋蒸(旋蒸条件为100℃，真空度为-0.1MPa)，剩余约50ml溶液时，停止旋蒸，加入800ml重结晶溶剂正己烷，将混合液抽滤，取滤饼即为二氟磷酸锂粗品。将粗品于真空烘箱内烘干(干燥条件为100℃，真空度为30Pa)，最终得到纯净的二氟 磷酸锂产品，产品纯度99.92％，产品收率64.83％，水分为9.1ppm。Dissolve 2.3 mol of lithium hydroxide in 2.8 L of anhydrous ethylene glycol dimethyl ether and add it to the reaction kettle. After the temperature rises to 60°C, add 1 mol of bisdifluorophosphate dropwise. After the dropwise addition is completed in 2.5 hours, the reaction 1h, filter the product using a microporous filter membrane (0.45μm, PTFE material), take out the filtrate and perform rotary evaporation (rotary evaporation conditions are 100°C, vacuum degree is -0.1MPa). When about 50ml of solution remains, stop rotary evaporation and add Use 800 ml of recrystallization solvent n-hexane, filter the mixture with suction, and take the filter cake to obtain crude lithium difluorophosphate. The crude product is dried in a vacuum oven (drying conditions are 100°C, vacuum degree is 30Pa), and finally pure difluoride is obtained. Lithium phosphate product, product purity is 99.92%, product yield is 64.83%, and moisture is 9.1ppm.
对比例2Comparative example 2
与实施例1的区别在于，在釜式反应器制备二磷酸酯，其他操作步骤与实施例1完全相同，具体操作如下：The difference from Example 1 is that the diphosphate ester is prepared in a kettle reactor, and other operating steps are exactly the same as Example 1. The specific operations are as follows:
将9.2mol乙二醇与0.6g酯化催化剂对甲苯磺酸(cas 6192-52-5)于反应瓶内常温进行机械搅拌预混，得到乙二醇和催化剂对甲苯磺酸的混合液。将18mol磷酸溶液加入到反应釜内，将乙二醇和催化剂对甲苯磺酸的混合液加入滴液漏斗内，待反应釜内温度达到50℃时，开始滴加，控制2h滴完，继续搅拌反应2h，冷却降温，得到含二磷酸酯、磷酸酯、水及其他杂质的反应液。将反应液进行精馏提纯(精馏条件为110℃，真空度30Pa，回流比选择6)，得到二磷酸酯产品收率72.6％，纯度99.1％，二磷酸酯密封放置备用。9.2 mol of ethylene glycol and 0.6 g of esterification catalyst p-toluenesulfonic acid (cas 6192-52-5) were mechanically stirred and premixed at room temperature in the reaction bottle to obtain a mixed solution of ethylene glycol and catalyst p-toluenesulfonic acid. Add 18 mol of phosphoric acid solution into the reaction kettle, and add the mixture of ethylene glycol and catalyst p-toluenesulfonic acid into the dropping funnel. When the temperature in the reaction kettle reaches 50°C, start dripping, control the dripping for 2 hours, and continue stirring the reaction. After cooling for 2 hours, the reaction solution containing diphosphate, phosphate, water and other impurities was obtained. The reaction solution was subjected to distillation and purification (distillation conditions were 110°C, vacuum degree 30Pa, reflux ratio selected 6) to obtain a diphosphate product with a yield of 72.6% and a purity of 99.1%. The diphosphate was sealed and placed for later use.
取11.25mol无水氟化铵加入到球磨机中，于500rpm的转速下进行球磨，过300目不锈钢筛网进行筛分，取筛下物活化无水氟化铵10.5mol，将其加入到反应釜内，随后加入无水乙腈3.75L进行保护，升至85℃后，加入0.12g催化剂五氟化锑。随后，将2.25mol二磷酸酯进行滴加，2h滴加完成后，反应3h。待反应产物冷却后，将其在120℃，10Pa，回流比4的条件下进行精馏，得到双二氟磷酸酯产品收率91.9％，纯度99.5％，并将双二氟磷酸酯进行绝水保存。Take 11.25 mol of anhydrous ammonium fluoride and add it to the ball mill, conduct ball milling at a speed of 500 rpm, sieve through a 300 mesh stainless steel screen, take 10.5 mol of activated anhydrous ammonium fluoride under the sieve, and add it to the reaction kettle within, then add 3.75L of anhydrous acetonitrile for protection. After rising to 85°C, add 0.12g of catalyst antimony pentafluoride. Subsequently, 2.25 mol of diphosphate was added dropwise. After the dropwise addition was completed in 2 hours, the reaction was continued for 3 hours. After the reaction product is cooled, it is distilled under the conditions of 120°C, 10Pa, and reflux ratio 4 to obtain the bisdifluorophosphate product with a yield of 91.9% and a purity of 99.5%, and the bisdifluorophosphate is dehydrated. save.
取2.3mol氢氧化锂溶解于2.8L无水乙二醇二甲醚内，加入反应釜中，待温度升至60℃后，滴加1mol双二氟磷酸酯，2.5h滴加完成后，反应1h，将产物利用微孔滤膜(0.45μm，PTFE材质)过滤，滤液取出进行旋蒸(旋蒸条件为100℃，真空度为-0.1MPa)，剩余约50ml溶液时，停止旋蒸，加入800ml重结晶溶剂正己烷，将混合液抽滤，取滤饼即为二氟磷酸锂粗品。将粗品于 真空烘箱内烘干(干燥条件为100℃，真空度为30Pa)，最终得到纯净的二氟磷酸锂产品，产品纯度99.87％，产品收率54.74％，水分为8.6ppm。Dissolve 2.3 mol of lithium hydroxide in 2.8 L of anhydrous ethylene glycol dimethyl ether and add it to the reaction kettle. After the temperature rises to 60°C, add 1 mol of bisdifluorophosphate dropwise. After the dropwise addition is completed in 2.5 hours, the reaction 1h, filter the product using a microporous filter membrane (0.45μm, PTFE material), take out the filtrate and perform rotary evaporation (rotary evaporation conditions are 100°C, vacuum degree is -0.1MPa). When about 50ml of solution remains, stop rotary evaporation and add Use 800 ml of recrystallization solvent n-hexane, filter the mixture with suction, and take the filter cake to obtain crude lithium difluorophosphate. put crude products in Dry in a vacuum oven (drying conditions are 100°C, vacuum degree is 30Pa), and finally a pure lithium difluorophosphate product is obtained, with a product purity of 99.87%, a product yield of 54.74%, and a moisture content of 8.6ppm.
以上所述仅是本申请的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本申请原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本申请的保护范围。 The above are only the preferred embodiments of the present application. It should be pointed out that for those of ordinary skill in the art, several improvements and modifications can be made without departing from the principles of the present application. These improvements and modifications can also be made. should be regarded as the scope of protection of this application.

Claims (10)

  1. 一种二氟磷酸锂的制备方法，其特征在于，包括如下步骤：A method for preparing lithium difluorophosphate, which is characterized in that it includes the following steps:
    1)将乙二醇和催化剂对甲苯磺酸的混合液，以及磷酸分别通入微通道反应器内进行反应，得到含二磷酸酯的混合物；1) Pass the mixture of ethylene glycol, catalyst p-toluenesulfonic acid, and phosphoric acid into the microchannel reactor for reaction to obtain a mixture containing diphosphate;
    2)将含二磷酸酯的混合物进行精馏提纯，得到二磷酸酯；2) Distillate and purify the mixture containing diphosphate to obtain diphosphate;
    3)将活化后的无水氟化剂、五氟化锑和无水有机溶剂混合，滴加二磷酸酯，滴加完成后进行反应，得到双二氟磷酸酯；3) Mix the activated anhydrous fluorinating agent, antimony pentafluoride and anhydrous organic solvent, add the diphosphate ester dropwise, and react after the addition is completed to obtain bisdifluorophosphate;
    4)在锂源和无水乙二醇二甲醚的混合液中滴加双二氟磷酸酯，滴加完成后进行反应，得到二氟磷酸锂。4) Add bisdifluorophosphate dropwise to the mixture of lithium source and anhydrous ethylene glycol dimethyl ether, and react after completion of the dropwise addition to obtain lithium difluorophosphate.
  2. 根据权利要求1所述的制备方法，其特征在于，步骤1)中所述乙二醇与催化剂对甲苯磺酸的摩尔质量比为1mol:(0.05～0.1)g；所述乙二醇与磷酸的摩尔比为1:(2.0～2.5)。The preparation method according to claim 1, characterized in that the molar mass ratio of ethylene glycol and catalyst p-toluenesulfonic acid in step 1) is 1 mol: (0.05~0.1) g; the ethylene glycol and phosphoric acid The molar ratio is 1:(2.0~2.5).
  3. 根据权利要求1所述的制备方法，其特征在于，步骤1)中乙二醇和催化剂对甲苯磺酸的混合液进料速度为30～40ml/min，磷酸的进料速度为70～100ml/min；在微通道反应器内进行反应时，反应的温度为40～50℃。The preparation method according to claim 1, characterized in that in step 1), the feeding speed of the mixed liquid of ethylene glycol and catalyst p-toluenesulfonic acid is 30-40ml/min, and the feeding speed of phosphoric acid is 70-100ml/min. ; When the reaction is carried out in a microchannel reactor, the reaction temperature is 40 to 50°C.
  4. 根据权利要求1所述的制备方法，其特征在于，步骤2)中精馏提纯时的温度为90～120℃，真空度为30～100Pa，回流比为4～6。The preparation method according to claim 1, characterized in that the temperature during distillation and purification in step 2) is 90-120°C, the vacuum degree is 30-100 Pa, and the reflux ratio is 4-6.
  5. 根据权利要求1所述的制备方法，其特征在于，步骤3)中所述无水氟化剂为无水氟化铵和/或无水氟化氢铵；所述无水氟化剂的活化方法为将无水氟化剂进行球磨、过筛；所述球磨的转速为500～800rpm；所述过筛用筛网孔径为200～500目。The preparation method according to claim 1, characterized in that the anhydrous fluorinating agent in step 3) is anhydrous ammonium fluoride and/or anhydrous ammonium bifluoride; the activation method of the anhydrous fluorinating agent is The anhydrous fluorinating agent is ball milled and sieved; the rotation speed of the ball mill is 500-800 rpm; the sieve mesh aperture is 200-500 mesh.
  6. 根据权利要求1所述的制备方法，其特征在于，步骤3)中所述活化后的无水氟化剂与二磷酸酯的摩尔比为(4.5～5.0)：1；所述二磷酸酯与五氟 化锑的摩尔质量比为1mol：(0.03～0.08)g；所述无水有机溶剂为无水四氢呋喃、无水乙腈、无水N，N-二甲基甲酰胺中的一种，无水有机溶剂的添加量为每摩尔二磷酸酯添加1L～2L无水有机溶剂。The preparation method according to claim 1, characterized in that the molar ratio of the activated anhydrous fluorinating agent and the diphosphate in step 3) is (4.5-5.0):1; the diphosphate and Pentafluoride The molar mass ratio of antimony is 1 mol: (0.03~0.08) g; the anhydrous organic solvent is one of anhydrous tetrahydrofuran, anhydrous acetonitrile, and anhydrous N, N-dimethylformamide. The amount of solvent added is 1L to 2L of anhydrous organic solvent per mole of diphosphate.
  7. 根据权利要求1所述的制备方法，其特征在于，步骤3)中二磷酸酯的滴加速度为每摩尔液体滴加0.5～2h，所述反应的温度为85～100℃，滴加完成后进行反应的时间为3～5h。The preparation method according to claim 1, characterized in that the dropping speed of the diphosphate in step 3) is 0.5 to 2 hours per mole of liquid, and the temperature of the reaction is 85 to 100°C, and is carried out after the dropwise addition is completed. The reaction time is 3 to 5 hours.
  8. 根据权利要求1所述的制备方法，其特征在于，步骤4)中所述锂源为氢氧化锂，所述双二氟磷酸酯与锂源的摩尔比为1:(2.1～3)；所述双二氟磷酸酯与无水乙二醇二甲醚的摩尔体积比为1mol:(2.5～3)L。The preparation method according to claim 1, wherein the lithium source in step 4) is lithium hydroxide, and the molar ratio of the bisdifluorophosphate to the lithium source is 1: (2.1-3); The molar volume ratio of the bisdifluorophosphate and anhydrous ethylene glycol dimethyl ether is 1 mol: (2.5-3) L.
  9. 根据权利要求1所述的制备方法，其特征在于，步骤4)中，所述双二氟磷酸酯的滴加速度为每摩尔滴加2～3h；所述反应的温度为50～70℃，滴加完成后进行反应的时间为1～2h。The preparation method according to claim 1, characterized in that in step 4), the dropping speed of the bisdifluorophosphate is 2 to 3 hours per mole; the temperature of the reaction is 50 to 70°C, The reaction time after the addition is completed is 1 to 2 hours.
  10. 根据权利要求1所述的制备方法，其特征在于，步骤4)中反应结束后，还包括纯化和干燥；所述纯化的方式为将反应产物依次进行过滤、旋蒸、重结晶和抽滤；所述旋蒸的条件为100～120℃，真空度-0.08～-0.1MPa；所述干燥的温度为80～120℃，真空度为30～80Pa。 The preparation method according to claim 1, characterized in that, after the reaction in step 4) is completed, it further includes purification and drying; the purification method is to sequentially filter, rotary evaporate, recrystallize and suction filtrate the reaction product; The rotary evaporation conditions are 100-120°C and the vacuum degree is -0.08~-0.1MPa; the drying temperature is 80-120°C and the vacuum degree is 30-80Pa.
PCT/CN2023/111387 2022-12-26 2023-08-07 Preparation method for lithium difluorophosphate WO2024008206A1 (en)

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