KR20220052558A - Preparation method of fluorosulfonylimide - Google Patents
Preparation method of fluorosulfonylimide Download PDFInfo
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- KR20220052558A KR20220052558A KR1020200136645A KR20200136645A KR20220052558A KR 20220052558 A KR20220052558 A KR 20220052558A KR 1020200136645 A KR1020200136645 A KR 1020200136645A KR 20200136645 A KR20200136645 A KR 20200136645A KR 20220052558 A KR20220052558 A KR 20220052558A
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Abstract
Description
본 발명은 플루오로설포닐이미드(HFSI)의 합성방법에 관한 것으로, 더욱 구체적으로 클로로설포닐이미드(HCSI)와 암모늄바이플로라이드 (ABF)로부터 에스테르, 에테르, 케톤용제를 사용하여 HFSI(클로로설포닐이미드)를 제조하는 방법에 관한 것이다.The present invention relates to a method for synthesizing fluorosulfonylimide (HFSI) , and more specifically, HFSI ( chlorosulfonylimide).
최근 전기, 전자, 통신 및 컴퓨터 산업이 급속히 발전함에 따라 고성능, 고안정성의 이차전지에 대한 수요가 점차 증가하고 있다. 특히, 이들 전자(통신)기기의 소형화, 경량화 추세에 따라 이 분야의 핵심부품인 리튬 이차전지의 박막화 및 소형화가 요구되고 있다.Recently, with the rapid development of electric, electronic, communication and computer industries, the demand for high-performance and high-stability secondary batteries is gradually increasing. In particular, in accordance with the trend of miniaturization and weight reduction of these electronic (communication) devices, thin film and miniaturization of lithium secondary batteries, which are core components in this field, are required.
상기 리튬 이차전지의 전해질로는 비수성 유기 용매에 전해질염을 용해한 이온 전도성 비수전해액이 주로 사용되고 있다. 한편, 상기 전해질염으로 널리 사용되는 LiPF6와 같은 리튬염은 낮은 열 안전성과 수분 민감성 물질로서, 물과 반응하면 PF6의 가수 분해로 인해 부식성이 강한 HF를 형성한다. 이렇게 형성된 HF는 약염기성을 나타내는 전극 활물질과 자발적으로 반응하여 전극 활물질 성분을 용출시키고, 그 결과 전지의 노화를 초래한다. 또한, 양극표면에 불화리튬(LiF)을 형성하여 전극 내 전기저항을 증가시키고 가스를 발생시켜 전지의 수명 저하를 초래한다.As the electrolyte of the lithium secondary battery, an ion conductive non-aqueous electrolyte obtained by dissolving an electrolyte salt in a non-aqueous organic solvent is mainly used. On the other hand, lithium salts such as LiPF6, which are widely used as the electrolyte salt, have low thermal stability and are moisture-sensitive, and when reacted with water, HF is highly corrosive due to hydrolysis of PF6. The thus formed HF reacts spontaneously with the electrode active material exhibiting weak basicity to elute the electrode active material component, resulting in the aging of the battery. In addition, lithium fluoride (LiF) is formed on the surface of the anode to increase electrical resistance in the electrode and generate gas, thereby reducing the lifespan of the battery.
최근, 이러한 문제를 해결하기 위하여 LiPF6를 대체할 수 있는 전해질염에 대한 연구가 대두되고 있으며, 그 대표적인 물질로 리튬 이미드염이 제안되고 있다. 특히, 리튬 이미드염 중에서 리튬 비스(플루오로술포닐)이미드 염 (LiFSI)은 열적 안정성 및 수분 안전성이 높고, 부식성 및 점성도가 낮으며, 높은 전기전도도를 가지고 있어 고출력 조건과 낮은 온도에서도 우수한 성능을 구현할 수 있는 물질로 알려지면서, 그 수요가 점차 증가하고 있다. 하지만, 이러한 장점에도 불구하고 상기 리튬 비스(플루오로술포닐)이미드염은 다단계의 합성 과정을 거치기 때문에 제조 공정이 복잡해 원가 경쟁력 면에서 LiPF6에 비해 상용화가 어려운 실정이다.하기 반응식 2는 LiFSI의 제조공정을 보여주고 있다.Recently, in order to solve this problem, research on electrolyte salts capable of replacing LiPF6 has been on the rise, and lithium imide salts have been proposed as a representative material thereof. In particular, among lithium imide salts, lithium bis(fluorosulfonyl)imide salt (LiFSI) has high thermal and moisture stability, low corrosiveness and viscosity, and high electrical conductivity. As it is known as a material that can implement However, despite these advantages, since the lithium bis(fluorosulfonyl)imide salt undergoes a multi-step synthesis process, it is difficult to commercialize compared to LiPF6 in terms of cost competitiveness because the manufacturing process is complicated. showing the process.
[반응식 2] [Scheme 2]
[반응식 3] [Scheme 3]
1. NH4F : KR2019/1092, KR101718292, KR2015/119310, US2013/331609, US9233849, WO2020/99527, 1. NH4F : KR2019/1092, KR101718292, KR2015/119310, US2013/331609, US9233849, WO2020/99527,
2. KF : EP2894146, KR2015/39845, Zeitschrift fur Anorganische und Allgemeine Chemie, 2005, vol. 631, # 1, p. 55 - 59, US2004/97757, CN109336785, US2011/34716, WO2007/104144 2. KF : EP2894146, KR2015/39845, Zeitschrift fur Anorganische und Allgemeine Chemie, 2005, vol. 631, #1, p. 55 - 59, US2004/97757, CN109336785, US2011/34716, WO2007/104144
3. HF : CN107055493, CN109734633, WO2016/177765, US7919629, TWI519514, TWI624470 3. HF : CN107055493, CN109734633, WO2016/177765, US7919629, TWI519514, TWI624470
4. ZnF2 : US2012/41233, US2011/34716, WO2015/4220, US2011/34716, US2012/41233 4. ZnF2 : US2012/41233, US2011/34716, WO2015/4220, US2011/34716, US2012/41233
5. LiF : EP2894146, US2004/97757 5. LiF : EP2894146, US2004/97757
6. NaF : EP2894146, US2004/97757 6. NaF : EP2894146, US2004/97757
7. BiF3 : US8377406, US2017/141432, US2011/34716 7. BiF3 : US8377406, US2017/141432, US2011/34716
8. CuF2 : US2011/34716 8. CuF2 : US2011/34716
9. CsF : US2004/97757, EP2894146, 9. CsF : US2004/97757, EP2894146,
10. SbF3 : Inorganic Chemistry, 1998, vol. 37, # 24, p. 6295 - 6303 10. SbF3 : Inorganic Chemistry, 1998, vol. 37, # 24, p. 6295 - 6303
상기와 같은 문제를 해결하기 위하여, 본 발명의 기술적 과제는 반응 단계를 단순화한 동시에, 고순도 리튬 비스(플루오로술포닐)이미드염을 제조하는데 사용되어지는 플루오로설포닐이미드의 효율적인 제조방법을 제공하는 것을 목적으로 한다.In order to solve the above problems, the technical object of the present invention is to simplify the reaction step and at the same time provide an efficient method for preparing fluorosulfonylimide used for preparing high-purity lithium bis(fluorosulfonyl)imide salt. intended to provide
1. 본 발명은 하기 반응식 1로 대표되는 HCSI(클로로설포닐이미드)와 ABF(암모늄바이플로라이드)의 반응으로부터 HFSI(클로로설포닐이미드)를 제조하는 방법을 제공한다.One. The present invention provides a method for preparing HFSI (chlorosulfonylimide) from the reaction of HCSI (chlorosulfonylimide) and ABF (ammonium bifluoride) represented by Scheme 1 below.
[반응식 1] [Scheme 1]
2. 본 발명은 상기 1의 반응식 1에서 ABF는 1~2당량을 사용하여 HFSI(클로로설포닐이미드)를 제조하는 방법을 제공한다.2. The present invention provides a method for preparing HFSI (chlorosulfonylimide) using 1 to 2 equivalents of ABF in Scheme 1 above.
3. 본 발명은 상기 1의 반응식 1에서 에스테르, 에테르, 케톤용제를 사용하여 HFSI(클로로설포닐이미드)를 제조하는 방법을 제공한다.3. The present invention provides a method for preparing HFSI (chlorosulfonylimide) using an ester, ether, and ketone solvent in Scheme 1 of the above 1.
본 발명의 제조방법은 저렴한 원료를 사용하여 기존의 LiFSI를 낮은 가격으로 제조할 수 있으며, 반응 공정이 간단하고 온화하여 대량 생산에 매우 적합하다.The manufacturing method of the present invention can produce conventional LiFSI at a low price using inexpensive raw materials, and the reaction process is simple and gentle, so it is very suitable for mass production.
본 발명의 클로로설포닐이미드는 하기 반응식 4와 같은 공정으로 제조되어 질 수 있다.Chlorosulfonylimide of the present invention can be prepared by the process shown in Scheme 4 below.
[반응식 4] [Scheme 4]
Path 1은 클로로설포닐이소시아네이트와 클로로설폰산의 결합반응에 이은, 탈산산반응에 의해서 진행되며, 클로로설포닐이소시아네이트의 가격이 고가라는 문제가 있다.Path 1 proceeds by a deoxidation reaction following the bonding reaction of chlorosulfonyl isocyanate and chlorosulfonic acid, and there is a problem that the price of chlorosulfonyl isocyanate is high.
Path 2는 저가의 원재료를 이용하여 가격이 저가일 수 있으나, 과량의 염화수소 가스가 발생하여 설비의 부식 및 폐기물이 발생된다는 문제가 있다.Path 2 may have a low price by using low-cost raw materials, but there is a problem in that excessive hydrogen chloride gas is generated, which causes corrosion of equipment and waste.
바람직하게는 path 3가 가격 및 공정비용 측면에서 유리할 수 있다.Preferably, path 3 may be advantageous in terms of price and process cost.
본 발명의 플루오로설포닐 이미드는 하기 반응식 5와 같이 ABF(암모늄바이플로라이드)을 유기용제하에서 클로로설포닐이미드와 반응하여 제조하는 것을 특징으로 한다.The fluorosulfonyl imide of the present invention is characterized in that it is prepared by reacting ABF (ammonium bifluoride) with chlorosulfonylimide in an organic solvent as shown in Scheme 5 below.
용제는 에스테르 (에틸아세테이트, 프로필아세테이트, 부틸아세테이트), 케톤 (메틸에텔케톤, 메틸이소프로필케톤, 메틸이소부틸케톤), 에테르 등이 사용되어 질수 있다.As the solvent, ester (ethyl acetate, propyl acetate, butyl acetate), ketone (methyl ether ketone, methyl isopropyl ketone, methyl isobutyl ketone), ether, etc. can be used.
또한, 하기 반응식 5의 ABF(암코늄바이플루오라이드)는 수분함량이 5%이하 인 것을 사용하는 것이 바람직하다. 수분률이 높으면 클로로설포닐이미드가 가수분해된 술폰산 부생성물의 함량이 증가하여 수율 및 순도가 저하되는 문제가 있다.In addition, it is preferable to use a water content of 5% or less as ABF (amconium bifluoride) in Scheme 5 below. When the moisture content is high, the content of sulfonic acid by-products hydrolyzed by chlorosulfonylimide increases, so that there is a problem in that the yield and purity are lowered.
[반응식 5] [Scheme 5]
본 발명은 기존에 불소화 반응에 사용되었던, NH4F, KF, HF, ZnF2, LiF, NaF, BiF3, CuF2, CsF, SbF3 등의 불소화 시약대비, 저가화 가능성, 안전성, 반응성, 수율향상 등에 장점이 있다.The present invention has advantages in lower cost, safety, reactivity, yield improvement, etc. compared to fluorination reagents such as NH4F, KF, HF, ZnF2, LiF, NaF, BiF3, CuF2, CsF, SbF3, which were previously used in the fluorination reaction.
Claims (3)
[반응식 1]
A method for preparing HFSI (chlorosulfonylimide) from the reaction of HCSI (chlorosulfonylimide) and ABF (ammonium bifluoride) represented by Scheme 1 below.
[Scheme 1]
In Reaction Scheme 1 of claim 1, ABF is a method for preparing HFSI (chlorosulfonylimide) using 1 to 2 equivalents.
A method for preparing HFSI (chlorosulfonylimide) using an ester, ether, or ketone solvent in Scheme 1 of claim 1 above.
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