KR102219684B1 - A method for preparing litium difluorophosphate - Google Patents
A method for preparing litium difluorophosphate Download PDFInfo
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- KR102219684B1 KR102219684B1 KR1020200047439A KR20200047439A KR102219684B1 KR 102219684 B1 KR102219684 B1 KR 102219684B1 KR 1020200047439 A KR1020200047439 A KR 1020200047439A KR 20200047439 A KR20200047439 A KR 20200047439A KR 102219684 B1 KR102219684 B1 KR 102219684B1
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- 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
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- C—CHEMISTRY; METALLURGY
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
Description
본 발명은 리튬디플루오로포스페이트의 제조방법에 관한 것으로서, 더욱 상세하게는 경제적이고 효율적으로 고순도의 리튬디플루오로포스페이트를 제조하는 방법에 관한 것이다.The present invention relates to a method for producing lithium difluorophosphate, and more particularly, to a method for producing high-purity lithium difluorophosphate economically and efficiently.
일반적으로 플루오로인산염은 클로로에틸렌 폴리머의 안정화제나 반응 윤활유의 촉매 또는 칫솔의 살균제, 그리고 목재의 보존제 등에 사용되고 있는 공업적으로 유용한 화합물로 알려져 있다.In general, fluorophosphate is known as an industrially useful compound used as a stabilizer for a chloroethylene polymer, a catalyst for a reaction lubricant, a disinfectant for a toothbrush, and a preservative for wood.
특히, 플루오로인산염 중에서 리튬디플루오로포스페이트는 전해액의 첨가제로 사용되고 있는데, 최근 전기 제품의 경량화와 소형화를 위한 소재로서 높은 에너지 밀도를 갖는 비수계 전해액 2차 전지의 개발에 활용되고 있다. 이러한 2차 전지는 리튬 이온 2차 전지의 적용 분야가 확대되면서 전지 특성을 개선하기 위하여 다양한 특성을 부여하는 방안이 연구되고 있다.In particular, among fluorophosphates, lithium difluorophosphate is used as an additive for electrolytes, and recently, it is used in the development of a nonaqueous electrolyte secondary battery having a high energy density as a material for weight reduction and miniaturization of electric products. As the application field of the lithium ion secondary battery is expanded, such a secondary battery is being studied to provide various characteristics to improve battery characteristics.
예컨대, 리튬 이온 2차 전지에 대하여 부하 특성, 사이클 특성, 보존 특성, 저온 특성 등의 전지 특성을 개선할 목적으로, 비수계 용매나 전해질에 대해 여러 가지 첨가성분이나 물성 개선을 위한 기술개발이 이루어지고 있다.For example, for the purpose of improving battery characteristics such as load characteristics, cycle characteristics, storage characteristics, and low-temperature characteristics for lithium ion secondary batteries, technology development has been made to improve various additive components or physical properties for non-aqueous solvents or electrolytes. Is losing.
그 중에서, 리튬디플루오로포스페이트는 비수계 전해액에 첨가되는 성분으로 저온 방전 특성, 대전류 방전 특성, 고온 보존 특성, 사이클 특성을 향상시키면서 안전성이 우수한 첨가제로서 크게 각광을 받고 있다.Among them, lithium difluorophosphate is a component added to a non-aqueous electrolyte, and has been in the spotlight as an additive with excellent safety while improving low-temperature discharge characteristics, high-current discharge characteristics, high-temperature storage characteristics, and cycle characteristics.
그러나 이렇게 리튬 2차 전지의 비수계 전해액에 첨가제로서 매우 유용한 리튬디플루오로포스페이트의 경우 다양한 제조방법이 제안되고 있으나, 제조공정이 복잡하거나 비경제적이고, 수율이 낮으며 순도가 좋지 못한 문제가 있다.However, in the case of lithium difluorophosphate, which is very useful as an additive to the non-aqueous electrolyte of a lithium secondary battery, various manufacturing methods have been proposed, but the manufacturing process is complicated or uneconomical, the yield is low, and the purity is poor.
종래기술의 예로서, 한국등록특허 제10-1539780호에서는 6불화인산염과 분자중에 Si-O-Si의 구조를 함유하는 성분을 반응시켜서 고순도의 디플루오로인산리튬을 제조하는 방법을 제안하고 있다.As an example of the prior art, Korean Patent Registration No. 10-1539780 proposes a method for producing high-purity lithium difluorophosphate by reacting hexafluorophosphate and a component containing a structure of Si-O-Si in the molecule. .
또한, 한국등록특허 제10-1887488호에서는 기존 제법의 제조 효율을 개선하기 위한 목적으로 리튬헥사플루오로포스페이트와 할로겐 원자를 함유하는 실리콘계 화합물을 이용하여 디플루오로인산리튬을 제조하는 방법을 제안하고 있다.In addition, Korean Patent No. 10-1887488 proposes a method of preparing lithium difluorophosphate using a silicon-based compound containing lithium hexafluorophosphate and a halogen atom for the purpose of improving the manufacturing efficiency of the existing manufacturing method. have.
그러나 이러한 기존의 제조방법들은 여전히 비경제적일 뿐만 아니라 수율과 순도가 낮아 그 제조방법에 개선의 여지가 많았다.However, these existing manufacturing methods are not only uneconomical, but also have low yield and purity, so there is much room for improvement in their manufacturing methods.
본 발명은 상기와 같은 종래 기술의 문제점을 개선하기 위하여, 새로운 반응공정을 개발하여 경제적이고 간편하면서도 고수율, 고순도로 리튬디플루오로포스페이트를 제조하는 것을 해결과제로 하여, 오랜 연구개발 끝에 새로운 제조방법을 개발하게 되었다.In order to improve the problems of the prior art as described above, the present invention is to develop a new reaction process to produce lithium difluorophosphate with high yield and high purity, economical and simple, as a solution. The method was developed.
따라서 본 발명의 목적은 고수율, 고순도로 리튬디플루오로포스페이트를 제조하는 방법을 제공하는데 있다.Accordingly, an object of the present invention is to provide a method for producing lithium difluorophosphate in high yield and high purity.
또한, 본 발명의 다른 목적은 종래에 비해 경제적이고 간단한 공정을 이용하는 새로운 공정을 통해 보다 효율적으로 리튬디플루오로포스페이트를 제조하는 방법을 제공하는데 있다.In addition, another object of the present invention is to provide a method for producing lithium difluorophosphate more efficiently through a new process using an economical and simple process compared to the prior art.
상기와 같은 본 발명의 과제 해결을 위하여, 본 발명은 리튬헥사플루오로포스페이트를 하기 화학식 1의 실란올과 반응시키고 여기에 수산화리튬을 반응시킨 다음 결정화하는 공정을 포함하는 리튬디플루오로포스페이트의 제조방법을 제공한다.In order to solve the problems of the present invention as described above, the present invention is to prepare lithium difluorophosphate including a step of reacting lithium hexafluorophosphate with silanol of the following formula (1), reacting lithium hydroxide thereto, and then crystallizing Provides a way.
[화학식 1][Formula 1]
상기 화학식 1에서 R1, R2, R3는 서로 같거나 다른 것으로서, 각각 수소원자, 수산기 또는 탄소수 1-6의 알킬기를 의미한다.In Formula 1, R 1 , R 2 , and R 3 are the same as or different from each other, and each means a hydrogen atom, a hydroxyl group, or an alkyl group having 1-6 carbon atoms.
본 발명의 바람직한 구현예에 따르면 좀 더 구체적으로는, 리튬헥사플루오로포스페이트를 알킬카보네이트에 용해하는 단계; According to a preferred embodiment of the present invention, more specifically, dissolving lithium hexafluorophosphate in an alkyl carbonate;
상기 리튬헥사플루오로포스페이트 용해 후에 상기 화학식 1의 실란올화합물을 첨가하여 반응시키는 단계; Reacting by adding the silanol compound of Formula 1 after dissolving the lithium hexafluorophosphate;
상기 반응이 완료된 후 수산화리튬을 첨가하여 반응시키는 단계; 및 Reacting by adding lithium hydroxide after the reaction is completed; And
수산화리튬 반응물을 결정화하여 리튬디플루오로포스페이트를 얻는 단계Crystallizing the lithium hydroxide reactant to obtain lithium difluorophosphate
를 포함하는 방법으로 리튬디플루오로포스페이트를 제조할 수 있다.Lithium difluorophosphate can be prepared by a method including.
본 발명의 바람직한 구현예에 따르면, 상기 화학식 1의 실란올 화합물은 트리메틸실란올, 다이메틸실란다이올, 메틸실란트리올 중에서 선택된 하나이상이 사용될 수 있다.According to a preferred embodiment of the present invention, the silanol compound of Formula 1 may be one or more selected from trimethylsilanol, dimethylsilanediol, and methylsilanetriol.
본 발명의 일 구현예에 따르면, 상기 화학식 1의 실란올 화합물을 반응시키는 단계에서는 50-80℃에서 상기 화학식 1의 실란올 화합물을 적가한 후 6-20시간동안 반응시키는 것이 바람직하다.According to an embodiment of the present invention, in the step of reacting the silanol compound of Formula 1, it is preferable to react for 6-20 hours after adding the silanol compound of Formula 1 dropwise at 50-80°C.
본 발명의 바람직한 구현예에 따르면, 상기 알킬카보네이트는 에틸메틸카보네이트, 디메틸카보네이트 중에서 하나이상을 사용할 수 있다.According to a preferred embodiment of the present invention, the alkyl carbonate may be one or more of ethyl methyl carbonate and dimethyl carbonate.
본 발명의 바람직한 구현예에 따르면, 수산화리튬을 첨가하여 반응시키는 단계에서는 상기 화학식 1의 실란올 화합물 반응 후 얻어진 반응물을 여과한 다음 그 여과물을 디메톡시에탄, 아세톤 또는 그 혼합물에 용해한 다음 수산화리튬을 첨가하여 반응시킬 수 있다.According to a preferred embodiment of the present invention, in the step of reacting by adding lithium hydroxide, the reaction product obtained after the reaction of the silanol compound of Formula 1 is filtered, and the filtrate is dissolved in dimethoxyethane, acetone, or a mixture thereof, and then lithium hydroxide. It can be reacted by adding.
본 발명의 바람직한 구현예에 따르면, 상기 결정화는 톨루엔, 클로로포름, 염화메틸렌, 노멀헥세인 중에서 선택된 하나 이상의 존재 하에 수행할 수 있다. According to a preferred embodiment of the present invention, the crystallization may be performed in the presence of at least one selected from toluene, chloroform, methylene chloride, and normal hexane.
본 발명의 바람직한 구현예에 따르면, 상기 제조방법은 불산함량을 100ppm 이하로 함유하는 리튬디플루오로포스페이트로 제조될 수 있다.According to a preferred embodiment of the present invention, the preparation method may be prepared with lithium difluorophosphate containing less than 100 ppm of hydrofluoric acid.
본 발명은 상기와 같은 리튬디플루오로포스페이트를 제조함에 있어서, 기존에 사용된 바 없는 상기 화학식 1의 실란올 화합물을 사용하여 제조함으로써, 제조공정이 용이하고, 특히 수율과 순도가 크게 향상되는 효과가 있다.In the present invention, in preparing lithium difluorophosphate as described above, by using the silanol compound of Formula 1, which has not been previously used, the manufacturing process is easy, and in particular, the yield and purity are greatly improved. There is.
또한, 이러한 본 발명의 새로운 제조방법을 통해 리튬디플루오로포스페이트를 기존에 비해 경제적으로 제조할 수 있어서 그 활용도를 더욱 높일 수 있는 효과가 있다.In addition, through the new manufacturing method of the present invention, lithium difluorophosphate can be produced economically compared to the existing one, and thus the utilization thereof can be further increased.
이하, 본 발명을 하나의 구현예로서 더욱 상세하게 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail as one embodiment.
본 발명은 리튬디플루오로포스페이트의 새로운 제조방법에 관한 것으로서, 하기 설명하는 구현예들은 본 발명을 상세히 설명하기 위한 하나의 참조일 뿐 본 발명이 이에 한정되는 것은 아니며, 여러 형태로 구현될 수 있다.The present invention relates to a new method for producing lithium difluorophosphate, and the embodiments described below are only one reference for describing the present invention in detail, and the present invention is not limited thereto, and may be implemented in various forms. .
본 발명은 리튬디플루오로포스페이트를 제조하기 위해 리튬헥사플루오로포스페이트와 하기 화학식 1의 실란올 화합물 및 수산화리튬을 이용하여 리튬디플루오로포스페이트를 제조하는 방법을 특징으로 하는 것이다.The present invention is characterized by a method of preparing lithium difluorophosphate using lithium hexafluorophosphate, a silanol compound of the following formula (1), and lithium hydroxide to prepare lithium difluorophosphate.
본 발명에서는 기존에 사용된 바 없는 실란올 화합물을 새롭게 적용함으로써, 종래에 비해 간단한 공정으로 용이하고 경제적으로 고순도의 목적물을 제조할 수 있다.In the present invention, by newly applying a silanol compound that has not been used previously, it is possible to easily and economically manufacture a high-purity target product with a simple process compared to the prior art.
본 발명은 리튬헥사플루오로포스페이트를 반응시키는 반응물로서, 하기 화학식 1의 실란올 화합물을 사용한다.In the present invention, as a reactant for reacting lithium hexafluorophosphate, a silanol compound represented by the following formula (1) is used.
[화학식 1][Formula 1]
상기 화학식 1에서 R1, R2, R3는 서로 같거나 다른 것으로서, 각각 수소원자, 수산기 또는 탄소수 1-6의 알킬기를 의미한다.In Formula 1, R 1 , R 2 , and R 3 are the same as or different from each other, and each means a hydrogen atom, a hydroxyl group, or an alkyl group having 1-6 carbon atoms.
그 다음으로, 그 반응물에 수산화리튬을 반응시킨 다음 결정화하는 공정을 거쳐서 리튬디플루오로포스페이트를 제조할 수 있다.Next, lithium difluorophosphate may be prepared through a process of reacting lithium hydroxide with the reactant and then crystallizing it.
이러한 본 발명의 제조방법을 좀더 구체적으로 설명하면 다음과 같다.The manufacturing method of the present invention will be described in more detail as follows.
본 발명에서는 출발물질로 통상 사용되었던, 리튬헥사플루오로포스페이트를 사용한다. 이러한 출발물질은 알킬카보네이트에 용해하여 사용한다.In the present invention, lithium hexafluorophosphate, which has been commonly used as a starting material, is used. These starting materials are dissolved in alkyl carbonate and used.
이때, 사용되는 용매인 알킬카보네이트로서는 예컨대, 에틸메틸카보네이트, 디메틸카보네이트 중에서 하나이상을 사용할 수 있다.At this time, as the alkyl carbonate used as the solvent, one or more of ethyl methyl carbonate and dimethyl carbonate may be used.
본 발명의 바람직한 구현예에 따르면, 상기 리튬헥사플루오로포스페이트를 용매에 용해한 후에 상기 화학식 1의 실란올 화합물을 첨가하여 반응시키는 단계를 거친다.According to a preferred embodiment of the present invention, after dissolving the lithium hexafluorophosphate in a solvent, a step of reacting by adding the silanol compound of Formula 1 is performed.
상기 화학식 1의 실란올 화합물은 통상의 방법으로 제조하여 사용할 수 있는데, 바람직하게는 트리메틸실란올, 다이메틸실란다이올, 메틸실란트리올 중에서 선택된 하나이상이 사용될 수 있다.The silanol compound of Formula 1 may be prepared and used by a conventional method, preferably at least one selected from trimethylsilanol, dimethylsilanediol, and methylsilanetriol may be used.
본 발명의 일 구현예에 따르면, 상기 화학식 1의 실란올 화합물을 반응시키는 단계에서는 상기 알킬카보네이트 용매에 용해된 리튬헥사플루오로포스페이트의 용액을 50-80℃, 더욱 바람직하게는 50-70℃로 승온하고, 이 온도 범위에서 상기 화학식 1의 실란올 화합물을 적가한 후 6-24시간, 더욱 바람직하게는 10-20시간 동안 교반 하에 반응시키는 것이 바람직하다.According to an embodiment of the present invention, in the step of reacting the silanol compound of Formula 1, a solution of lithium hexafluorophosphate dissolved in the alkyl carbonate solvent is 50-80°C, more preferably 50-70°C. After raising the temperature and adding the silanol compound of Formula 1 dropwise in this temperature range, it is preferable to react under stirring for 6 to 24 hours, more preferably 10 to 20 hours.
본 발명의 바람직한 구현예에 따르면, 상기 반응이 완료된 후에는 그 반응물에 수산화리튬을 첨가하여 반응시키는 단계를 거친다.According to a preferred embodiment of the present invention, after the reaction is completed, lithium hydroxide is added to the reaction product to react.
본 발명의 바람직한 구현예에 따르면, 수산화리튬을 첨가하여 반응시키는 단계에서는 상기 화학식 1의 실란올 화합물 반응 후 얻어진 반응물을, 바람직하게는 상온으로 냉각하고, 여과한 다음 그 여과물을 디메톡시에탄, 아세톤 또는 그 혼합물에 용해한 후 수산화리튬을 첨가하여 반응시킬 수 있다.According to a preferred embodiment of the present invention, in the step of reacting by adding lithium hydroxide, the reaction product obtained after the reaction of the silanol compound of Formula 1 is cooled to room temperature, filtered, and then the filtrate is dimethoxyethane, After dissolving in acetone or a mixture thereof, lithium hydroxide may be added to react.
이때, 바람직하게는 수산화리튬을 첨가한 다음 1-6시간, 바람직하게는 1-3시간동안 교반 하에 반응시키는 것이 좋다. 이렇게 반응시킨 다음에는 충분하게 반응이 완료되어 안정될 때까지 정치하는 것이 좋은데, 예컨대 3-12시간, 더욱 좋기로는 5-7시간동안 정치할 수 있다.At this time, preferably, lithium hydroxide is added and then reacted for 1-6 hours, preferably 1-3 hours under stirring. After reacting in this way, it is good to stand still until the reaction is sufficiently completed and stable, for example, it can be left to stand for 3-12 hours, more preferably for 5-7 hours.
본 발명에 따르면 이렇게 반응이 완료된 후에는, 수산화리튬 반응물을 결정화하여 리튬디플루오로포스페이트를 얻을 수 있다.According to the present invention, after the reaction is completed in this way, lithium difluorophosphate can be obtained by crystallizing the lithium hydroxide reactant.
본 발명의 바람직한 구현예에 따르면, 상기 결정화는 톨루엔, 클로로포름, 염화메틸렌, 노멀헥세인 중에서 선택된 하나 이상의 용매 존재 하에 수행할 수 있다. 결정화를 위한 용매는 반응액을 서서히 적가하면서 상온에서 30-2시간 교반하면서 결정화할 수 있다. 결정화 이후에는 여과 건조하여 목적물을 제조할 수 있다.According to a preferred embodiment of the present invention, the crystallization may be carried out in the presence of at least one solvent selected from toluene, chloroform, methylene chloride, and normal hexane. The solvent for crystallization may be crystallized while stirring at room temperature for 30-2 hours while gradually adding the reaction solution dropwise. After crystallization, it may be filtered and dried to prepare a target product.
특히, 본 발명에 따르면 이러한 결정화 과정을 거치게 되면 고순도의 리튬디플루오로포스페이트를 고수율로 제조할 수 있다.In particular, according to the present invention, if such a crystallization process is performed, lithium difluorophosphate of high purity can be prepared in high yield.
본 발명의 바람직한 구현예에 따르면, 본 발명의 전형적인 제조방법으로서는 예컨대 다음의 방법으로 제조할 수 있다.According to a preferred embodiment of the present invention, as a typical manufacturing method of the present invention, it can be manufactured by, for example, the following method.
즉, 구체적인 제저방법의 예로서, 리튬헥사플루오로포스페이트를 에틸메틸카보네이트에 용해하는 단계; That is, as an example of a specific production method, dissolving lithium hexafluorophosphate in ethyl methyl carbonate;
상기 리튬헥사플루오로포스페이트 용해 후에 상기 화학식 1의 실란올화합물로 트리메틸실란올을 첨가하여 반응시키는 단계; Reacting by adding trimethylsilanol to the silanol compound of Formula 1 after dissolving the lithium hexafluorophosphate;
상기 반응이 완료된 후 수산화리튬을 첨가하여 반응시키는 단계; 및 Reacting by adding lithium hydroxide after the reaction is completed; And
수산화리튬 반응물을 톨루엔 존재 하에 결정화하여 리튬디플루오로포스페이트를 얻는 단계Crystallization of a lithium hydroxide reactant in the presence of toluene to obtain lithium difluorophosphate
를 포함하는 방법으로 리튬디플루오로포스페이트를 제조할 수 있다.Lithium difluorophosphate can be prepared by a method including.
이러한 본 발명의 전형적인 일 구현예로서의 제조방법은 하기 반응식 1로 표시될 수 있다.The manufacturing method as a typical embodiment of the present invention can be represented by the following Scheme 1.
[반응식 1][Scheme 1]
이렇게 본 발명의 제조방법에 따라 제조된 리튬디플루오로포스페이트는 종래의 제조방법에 비해 불순물의 함량이 현저하게 적은데, 특히 부반응으로 생성되는 불산 함량이 크게 저하된다.Thus, the lithium difluorophosphate prepared according to the production method of the present invention has significantly less impurities than the conventional production method, and in particular, the content of hydrofluoric acid generated by side reactions is greatly reduced.
본 발명의 바람직한 구현예에 따르면, 상기 제조방법에 의해 제조된 리튬디플루오로포스페이트는 불산 함량이 100ppm 이하, 더 바람직하게는 80ppm, 이하, 50ppm 이하, 더 좋기로는 20ppm 이하, 10ppm이하, 가장 좋기로는 5ppm 이하로 함유되는 고순도의 목적물로 제조될 수 있다.According to a preferred embodiment of the present invention, the lithium difluorophosphate prepared by the above manufacturing method has a hydrofluoric acid content of 100 ppm or less, more preferably 80 ppm, or less, 50 ppm or less, more preferably 20 ppm or less, 10 ppm or less, most Preferably, it can be prepared as a high-purity target product containing less than 5ppm.
또한, 본 발명에 따르면 수율이 90% 이상의 고수율로 제조되면서도 불산함량이 100ppm 이하로 함유되고 순도가 99.5% 이상, 더 바람직하게는 순도99.85% 이상을 가지는 고순도, 고품질의 리튬디플루오로포스페이트를 제조할 수 있다.In addition, according to the present invention, a high-purity, high-quality lithium difluorophosphate containing a hydrofluoric acid content of 100 ppm or less and a purity of 99.5% or more, and more preferably a purity of 99.85% or more while being manufactured in a high yield of 90% or more is prepared. Can be manufactured.
이와 같이, 본 발명은 새로운 반응물로 실란올 화합물을 사용함으로써, 종래에 비해 간단하고 경제적인 공정으로 고수율, 고순도의 리튬디플루오로포스페이트를 제조할 수 있는 것이다.As described above, in the present invention, by using a silanol compound as a new reactant, lithium difluorophosphate with high yield and high purity can be prepared in a simple and economical process compared to the conventional one.
이상에서 설명한 바와 같은 본 발명은 하기의 실시예에 의하여 더욱 자세하게 설명하겠는 바, 본 발명이 다음 실시예에 의하여 한정되는 것은 아니다.The present invention as described above will be described in more detail by the following examples, but the present invention is not limited by the following examples.
실시예 1Example 1
리튬헥사플루오로포스페이트 400g을 에틸메틸카보네이트 2400g에 녹이고 정제수 3g을 적가한 후 60℃까지 승온한다. 트리메틸실란올 522g을 60℃에서 적가한 후 12시간동안 반응시킨다. 반응이 완료 된 후 냉각하여 여과하고 여과 습체를 디메톡시에탄 1200g에 용해시킨다. 용해액에 수산화리튬 4g을 넣고 2시간동안 교반하고 6시간동안 정치한다. 400 g of lithium hexafluorophosphate was dissolved in 2400 g of ethyl methyl carbonate, 3 g of purified water was added dropwise, and the temperature was raised to 60°C. After adding 522 g of trimethylsilanol dropwise at 60° C., it was reacted for 12 hours. After the reaction is complete, it is cooled, filtered, and the filter wet is dissolved in 1200 g of dimethoxyethane. 4 g of lithium hydroxide was added to the solution, stirred for 2 hours, and allowed to stand for 6 hours.
반응액을 여과한 후 여액을 농축하고 톨루엔 2400g을 적가하여 결정화 한다. 이후 여과하고 건조하여 리튬디플루오로포스페이트를 264g을 얻었다. (수율 : 93%, 불산농도 : 2.1ppm, 순도 : 99.99%)After the reaction solution was filtered, the filtrate was concentrated, and 2400 g of toluene was added dropwise to crystallize. After filtration and drying, 264 g of lithium difluorophosphate was obtained. (Yield: 93%, hydrofluoric acid concentration: 2.1ppm, purity: 99.99%)
실시예 2 Example 2
에틸메틸카보네이트를 대신하여 다이메틸카보네이트를 사용하였으며, 이외에는 상기 실시예 1과 동일하게 실시하였다. 리튬디플루오로포스페이트를 264g 얻었다, (수율 : 93%, 불산농도 : 3.0ppm, 순도 : 99.99%)Dimethyl carbonate was used in place of ethyl methyl carbonate, except that it was carried out in the same manner as in Example 1. 264 g of lithium difluorophosphate was obtained, (yield: 93%, hydrofluoric acid concentration: 3.0 ppm, purity: 99.99%)
실시예 3Example 3
리튬헥사플루오로포스페이트 400g을 에틸메틸카보네이트 2400g에 녹이고 정제수 3g을 적가한 후 60℃까지 승온한다. 다이메틸실란다이올 261g을 60℃에서 적가한 후 12시간동안 반응시킨다. 반응이 완료 된 후 냉각하여 여과하고 여과 습체를 디메톡시에탄 1200g에 용해시킨다. 용해액에 수산화리튬 4g을 넣고 2시간동안 교반하고 6시간동안 정치한다. 400 g of lithium hexafluorophosphate was dissolved in 2400 g of ethyl methyl carbonate, 3 g of purified water was added dropwise, and the temperature was raised to 60°C. After 261 g of dimethylsilanediol was added dropwise at 60°C, it was reacted for 12 hours. After the reaction is complete, it is cooled, filtered, and the filter wet is dissolved in 1200 g of dimethoxyethane. 4 g of lithium hydroxide was added to the solution, stirred for 2 hours, and allowed to stand for 6 hours.
반응액을 여과한 후 여액을 농축하고 톨루엔 2400g을 적가하여 결정화 한다. 이후 여과하고 건조하여 리튬디플루오로포스페이트를 262g을 얻었다. (수율 : 92%, 불산농도 : 2.1ppm, 순도 : 99.99%)After the reaction solution was filtered, the filtrate was concentrated, and 2400 g of toluene was added dropwise to crystallize. After filtration and drying, 262g of lithium difluorophosphate was obtained. (Yield: 92%, hydrofluoric acid concentration: 2.1ppm, purity: 99.99%)
실시예 4Example 4
리튬헥사플루오로포스페이트 400g을 에틸메틸카보네이트 2400g에 녹이고 정제수 3g을 적가한 후 60℃까지 승온한다. 메틸실란트리올 174g을 60℃에서 적가한 후 12시간동안 반응시킨다. 반응이 완료 된 후 냉각하여 여과하고 여과 습체를 디메톡시에탄 1200g에 용해시킨다. 용해액에 수산화리튬 4g을 넣고 2시간동안 교반하고 6시간동안 정치한다. 400 g of lithium hexafluorophosphate was dissolved in 2400 g of ethyl methyl carbonate, 3 g of purified water was added dropwise, and the temperature was raised to 60°C. After 174 g of methylsilanetriol was added dropwise at 60°C, it was reacted for 12 hours. After the reaction is complete, it is cooled, filtered, and the filter wet is dissolved in 1200 g of dimethoxyethane. 4 g of lithium hydroxide was added to the solution, stirred for 2 hours, and allowed to stand for 6 hours.
반응액을 여과한 후 여액을 농축하고 톨루엔 2400g을 적가하여 결정화 한다. 이후 여과하고 건조하여 리튬디플루오로포스페이트를 264g을 얻었다. (수율 : 93%, 불산농도 : 2.2ppm, 순도 : 99.99%)After the reaction solution was filtered, the filtrate was concentrated, and 2400 g of toluene was added dropwise to crystallize. After filtration and drying, 264 g of lithium difluorophosphate was obtained. (Yield: 93%, hydrofluoric acid concentration: 2.2ppm, purity: 99.99%)
실시예 5 - 7Examples 5-7
수산화리튬의 사용량을 각각 2g, 6g, 10g 첨가하는 것 외에는 상기 실시예 1과 동일하게 실시하였다. It was carried out in the same manner as in Example 1, except that 2g, 6g, and 10g of lithium hydroxide were added respectively.
그 결과 제조된 리튬디플루오로포스페이트는 각각 다음과 같은 수율과 순도를 나타내었다.As a result, the prepared lithium difluorophosphate showed the following yield and purity, respectively.
실시예 5 (수율 : 93%, 불산농도 : 9.8ppm, 순도 : 99.99%) Example 5 (yield: 93%, hydrofluoric acid concentration: 9.8ppm, purity: 99.99%)
실시예 6 (수율 : 92%, 불산농도 : 2.0ppm, 순도 : 99.98%)Example 6 (yield: 92%, hydrofluoric acid concentration: 2.0 ppm, purity: 99.98%)
실시예 7 (수율 : 93% 불산농도 : 1.8ppm, 순도 : 99.90%)Example 7 (yield: 93% hydrofluoric acid concentration: 1.8 ppm, purity: 99.90%)
실시예 8Example 8
디메톡시에탄를 대신 하여 아세톤을 사용하였으며, 이외에는 상기 실시예 1과 동일하게 실시하였다. 이렇게 하여 리튬디플루오로포스페이트를 262g을 얻었다. (수율 : 92%, 불산농도 : 2.8ppm, 순도 : 99.98%)Acetone was used in place of dimethoxyethane, except that it was carried out in the same manner as in Example 1 above. In this way, 262 g of lithium difluorophosphate was obtained. (Yield: 92%, hydrofluoric acid concentration: 2.8ppm, purity: 99.98%)
실시예 9 - 11Examples 9-11
최종 결정화 과정에서 톨루엔을 대신 하여 비극성 용매로 클로로포름, 염화메틸렌, 노멀헥세인을 각각 사용하였으며, 그 이외에는 상기 실시예 1과 동일하게 실시하였다. In the final crystallization process, chloroform, methylene chloride, and normal hexane were respectively used as non-polar solvents in place of toluene, except for that in the same manner as in Example 1 above.
그 결과 제조된 리튬디플루오로포스페이트는 각각 다음과 같은 수율과 순도를 나타내었다.As a result, the prepared lithium difluorophosphate showed the following yield and purity, respectively.
실시예 9 (수율 : 91%, 불산농도 : 2.2ppm, 순도 : 99.99%) Example 9 (yield: 91%, hydrofluoric acid concentration: 2.2 ppm, purity: 99.99%)
실시예 10 (수율 : 92%, 불산농도 : 2.1ppm, 순도 : 99.98%)Example 10 (yield: 92%, hydrofluoric acid concentration: 2.1 ppm, purity: 99.98%)
실시예 11 (수율 : 90%, 불산농도 : 2.3ppm, 순도 : 99.91%)Example 11 (yield: 90%, hydrofluoric acid concentration: 2.3 ppm, purity: 99.91%)
비교예 1Comparative Example 1
리튬헥사플루오로포스페이트 400g을 에틸메틸카보네이트 2400g에 녹이고 정제수 3g을 적가한 후 60℃까지 승온한다. 트리메틸실란올 522g을 60℃에서 적가한 후 12시간동안 반응시킨다. 반응이 완료 된 후 냉각하여 여과하고 건조하여 리튬디플루오로포스페이트를 272g을 얻었다. (수율 : 96%, 불산농도 : 358ppm, 순도 : 99.82%)400 g of lithium hexafluorophosphate was dissolved in 2400 g of ethyl methyl carbonate, 3 g of purified water was added dropwise, and the temperature was raised to 60°C. After adding 522 g of trimethylsilanol dropwise at 60° C., it was reacted for 12 hours. After the reaction was completed, it was cooled, filtered, and dried to obtain 272 g of lithium difluorophosphate. (Yield: 96%, hydrofluoric acid concentration: 358ppm, purity: 99.82%)
비교예 2Comparative Example 2
리튬헥사플루오로포스페이트 400g을 에틸메틸카보네이트 2400g에 녹이고 정제수 3g을 적가한 후 60℃까지 승온한다. 트리메틸실란올 522g을 60℃에서 적가한 후 12시간동안 반응시킨다. 반응이 완료 된 후 냉각하여 여과하고 여과 습체를 디메톡시에탄 1200g에 용해시킨다. 400 g of lithium hexafluorophosphate was dissolved in 2400 g of ethyl methyl carbonate, 3 g of purified water was added dropwise, and the temperature was raised to 60°C. After adding 522 g of trimethylsilanol dropwise at 60° C., it was reacted for 12 hours. After the reaction is complete, it is cooled, filtered, and the filter wet is dissolved in 1200 g of dimethoxyethane.
용해액을 농축하고 톨루엔 2400g을 적가하여 결정화 한다. 이후 여과하고 건조하여 리튬디플루오로포스페이트를 267g을 얻었다. (수율 : 94%, 불산농도 : 137ppm, 순도 : 99.97%)The solution is concentrated, and 2400 g of toluene is added dropwise to crystallize. After filtration and drying, 267 g of lithium difluorophosphate was obtained. (Yield: 94%, hydrofluoric acid concentration: 137ppm, purity: 99.97%)
비교예 3Comparative Example 3
리튬헥사플루오로포스페이트 400g을 에틸메틸카보네이트 2400g에 녹이고 60℃까지 승온한다. 트리메틸실란올 522g을 60℃에서 적가한 후 12시간동안 반응시킨다. 반응이 완료 된 후 냉각하여 여과하고 건조하여 리튬디플루오로포스페이트를 272g을 얻었다. (수율 : 96%, 불산농도 : 1600ppm, 순도 : 98.71)400 g of lithium hexafluorophosphate was dissolved in 2400 g of ethyl methyl carbonate, and the temperature was raised to 60°C. After adding 522 g of trimethylsilanol dropwise at 60° C., it was reacted for 12 hours. After the reaction was completed, it was cooled, filtered, and dried to obtain 272 g of lithium difluorophosphate. (Yield: 96%, hydrofluoric acid concentration: 1600ppm, purity: 98.71)
비교예 4Comparative Example 4
리튬헥사플루오로포스페이트 400g을 에틸메틸카보네이트 2400g에 녹이고 정제수 6g을 적가한 후 60℃까지 승온한다. 트리메틸실란올 522g을 60℃에서 적가한 후 12시간동안 반응시킨다. 반응이 완료 된 후 냉각하여 여과하고 건조하여 리튬디플루오로포스페이트를 258g을 얻었다. (수율 : 90%, 불산농도 : 345ppm, 순도 : 99.88%)400 g of lithium hexafluorophosphate was dissolved in 2400 g of ethyl methyl carbonate, 6 g of purified water was added dropwise, and the temperature was raised to 60°C. After adding 522 g of trimethylsilanol dropwise at 60° C., it was reacted for 12 hours. After the reaction was completed, it was cooled, filtered, and dried to obtain 258 g of lithium difluorophosphate. (Yield: 90%, hydrofluoric acid concentration: 345ppm, purity: 99.88%)
Claims (8)
[화학식 1]
상기 화학식 1에서 R1, R2, R3는 서로 같거나 다른 것으로서, 각각 수소원자, 수산기 또는 탄소수 1-6의 알킬기를 의미한다.
A method for preparing lithium difluorophosphate comprising a step of reacting lithium hexafluorophosphate with a silanol compound of the following formula (1), reacting lithium hydroxide thereto, and then crystallizing:
[Formula 1]
In Formula 1, R 1 , R 2 , and R 3 are the same as or different from each other, and each means a hydrogen atom, a hydroxyl group, or an alkyl group having 1-6 carbon atoms.
상기 리튬헥사플루오로포스페이트 용해 후에 하기 화학식 1의 실란올 화합물을 첨가하여 반응시키는 단계;
상기 반응이 완료된 후 수산화리튬을 첨가하여 반응시키는 단계; 및
수산화리튬 반응물을 결정화하여 리튬디플루오로포스페이트를 얻는 단계
를 포함하는 리튬디플루오로포스페이트의 제조방법:
[화학식 1]
상기 화학식 1에서 R1, R2, R3는 서로 같거나 다른 것으로서, 각각 수소원자, 수산기 또는 탄소수 1-6의 알킬기를 의미한다.
Dissolving lithium hexafluorophosphate in alkyl carbonate;
Reacting by adding a silanol compound of the following formula (1) after dissolving the lithium hexafluorophosphate;
Reacting by adding lithium hydroxide after the reaction is completed; And
Crystallizing the lithium hydroxide reactant to obtain lithium difluorophosphate
Method for producing lithium difluorophosphate comprising:
[Formula 1]
In Formula 1, R 1 , R 2 , and R 3 are the same as or different from each other, and each means a hydrogen atom, a hydroxyl group, or an alkyl group having 1-6 carbon atoms.
The method of claim 2, wherein the silanol compound of Formula 1 is at least one selected from trimethylsilanol, dimethylsilanediol, and methylsilanetriol.
The method of claim 2, wherein in the step of reacting the silanol compound of Formula 1, the silanol compound of Formula 1 is added dropwise at 50-80° C. and then reacted for 6-20 hours. Manufacturing method.
The method of claim 2, wherein the alkyl carbonate is at least one of ethyl methyl carbonate and dimethyl carbonate.
The method according to claim 2, wherein in the step of reacting by adding lithium hydroxide, the reaction product obtained after the reaction of the silanol compound of Formula 1 is filtered, and the filtrate is dissolved in dimethoxyethane, acetone or a mixture thereof, and lithium hydroxide is added. A method for producing lithium difluorophosphate, characterized in that reaction.
The method of claim 2, wherein the crystallization is performed in the presence of at least one solvent selected from toluene, chloroform, methylene chloride, and normal hexane.
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| KR102596526B1 (en) * | 2023-02-28 | 2023-10-31 | 이피캠텍 주식회사 | Manufactuiring method for crystallization of lithium difluorophosphate and Crystallization of lithium difluorophosphate |
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