CN103813980B - 用于制备硫化锂的方法 - Google Patents
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Abstract
本发明涉及用于制备硫化锂的新方法及其用途,其中在惰性条件下,在-20至120℃温度范围内,在非质子有机溶剂中进行含锂强碱与硫化氢的反应。根据该方法获得的硫化锂用作伽伐尼电池中的正极物料或用于合成传导Li-离子的固体,特别是用于合成玻璃、玻璃陶瓷或结晶产品。
Description
本发明涉及制备硫化锂的新方法及其用途。
最近,硫化锂作为用于合成传导锂离子的固体(玻璃、玻璃陶瓷或结晶产品如锂-硫银锗矿)的原料或作为锂/硫电池组中的阴极材料受到关注。锂/硫-电池组与锂-离子-电池组相比具有明显更高的能量密度并因此在电动性领域中的潜在应用对此极感兴趣。
在盖墨林无机化学手册,锂,补充卷(1969)中描述了下面的用于制备硫化锂的方法:
·将锂金属和硫一起研磨;
·使硫化铵或硫与锂金属在液氨中发生反应;
·使乙醇锂与H2S在乙醇中发生反应。
在所有这些方法中都会产生或多或少的含多硫化物的产物混合物,有时必须对其进行复杂的纯化。因此已知的是,在大约500℃的温度下用碳或氢还原硫化锂。文献EP0802159A1描述了氢氧化锂与硫化氢在气相中在130至445℃的温度范围内的反应。文献US4126666A1也描述了碳酸锂与硫化氢在气相中在500-700℃的温度范围内的反应。
此外,从文献US3615191A1和US3642436A1已知锂金属或氢化锂与硫化氢在醚溶剂如四氢呋喃(THF)中的反应。在这些反应中,产生硫化锂(Li2S)和硫氢化锂(LiSH)的混合物。可以通过在180℃-200℃下的热处理使不希望的LiSH转化为Li2S和硫化氢。
最近,从文献EP1460039A1已知氢氧化锂或碳酸锂与硫化氢在作为溶剂的N-甲基吡咯烷酮中在130℃下首先转化为LiSH,然后在200℃下转化为Li2S。文献EP1681263A1提出,用有机溶剂在超过100℃的温度下洗涤通过氢氧化锂与硫化氢在非质子有机溶剂中的反应获得的Li2S,以提纯Li2S。
本发明的目的在于,提供一种简单的方法,借助于此方法可以在尽可能经济、简单的反应条件下制备高纯度的硫化锂。
根据本发明,所述目的通过这样的方法得以解决,其中使含锂强碱与硫化氢在非质子有机溶剂中,在-20至120℃的温度范围内,在惰性条件下,优选在0至80℃的温度范围内,进行反应。在本发明范围内,将惰性条件理解为在保护气体下排除空气和空气湿度的操作。
为此,将气态硫化氢导入在非质子溶剂中的含Li强碱的溶液中。该反应在室温下自发地开始并且是放热的。硫化锂作为白色固体析出并且可以在反应结束后通过过滤和干燥分离。所述含锂强碱选自烷基锂、芳基锂或氨基锂,并且按照下列的反应方程式反应:
2R-Li+H2S→Li2S+2RH
2R2N-Li+H2S→Li2S+2R2NH
经分离的材料在X射线衍射图中只显示出所希望的Li2S的线条,未能检测到副产物如LiSH。
优选地,所使用的含Li强碱是下述商购可得的物质或溶液:在烃中的丁基锂或己基锂,或在不同的非质子溶剂中的有机氨基锂,优选二异丙基氨基锂或六甲基二硅基氨基锂(Lithiumhexamethyldisilazid)。
典型的非质子溶剂为脂肪烃或芳香烃,优选己烷或甲苯,以及选自脂肪醚或环醚的醚溶剂,优选乙醚、THF或这些溶剂的混合物。
根据本发明的方法相对于现有技术的优点因此是:
·使用商购可得的原材料;
·避免用对空气敏感和对湿度敏感的固体如Li-金属或LiH操作;
·在温和温度下的反应操作,由此不需要额外的能量用于加热或冷却;
·通过简单的方法如过滤和干燥分离产物;
·获得纯相产物,这避免了进一步的纯化步骤如破坏LiSH的加热。
使用根据本发明获得的硫化锂作为伽伐尼电池中的正极物料,用于合成传导Li-离子的固体,特别是用于合成玻璃、玻璃陶瓷或结晶产品和特别优选用于合成Li-硫银锗矿。
实施例1:从硫化氢制备硫化锂
在具有温度传感器、气体导入管(潜管)和气体排出管道(经由气量表和洗气器)的惰性化过的3L-平法兰双层反应器中,在氩气气氛下,预先置入1000g(1449ml,3.47mol,1.0当量)正丁基锂(2.4M,在己烷中),随后添加另外的380ml己烷。在搅拌下,将该反应溶液冷却至10℃。随后在10-15℃下经3小时将总共59g(38.7L,1.73mol,0.5当量)硫化氢经由潜管输入到该反应溶液中。由此析出无色固体。为了保持该反应悬浮液可搅拌,总共添加另外550ml己烷。在气体导入结束后,将反应器内容物加热至室温(22℃)并搅拌另外2小时。随后,使反应悬浮液通过G3-玻璃料过滤并用多份己烷彻底洗涤残留的无色固体。将所获得的固体在高真空下在室温下进行干燥直至恒重,随后通过X射线粉末衍射法(XRD)进行分析。获得纯相的硫化锂。
Claims (4)
1.用于制备硫化锂的方法,其特征在于,在惰性条件下,在-20至120°C温度范围内,在非质子有机溶剂中进行选自烷基锂、芳基锂或氨基锂的含锂强碱与硫化氢的反应,其中使用脂肪烃、芳香烃或醚溶剂或这些溶剂的混合物作为非质子有机溶剂,其中惰性条件表示在保护气体下排除空气和空气湿度的操作。
2.根据权利要求1的方法,其特征在于,使用丁基锂、己基锂、二异丙基氨基锂或六甲基二硅基氨基锂作为含锂强碱。
3.根据权利要求1的方法,其特征在于,使用己烷、甲苯、乙醚或THF作为溶剂。
4.根据权利要求1或2的方法,其特征在于,在0至80°C的温度范围内进行所述反应。
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DE102011076572 | 2011-05-27 | ||
DE102011076572.7 | 2011-05-27 | ||
PCT/EP2012/060014 WO2012163900A2 (de) | 2011-05-27 | 2012-05-29 | Verfahren zur herstellung von lithiumsulfid |
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CN103813980B true CN103813980B (zh) | 2016-05-18 |
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US (1) | US9017582B2 (zh) |
EP (1) | EP2714587B1 (zh) |
JP (1) | JP6016899B2 (zh) |
KR (1) | KR101963297B1 (zh) |
CN (1) | CN103813980B (zh) |
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CN103329319B (zh) * | 2011-01-27 | 2017-08-29 | 出光兴产株式会社 | 碱金属硫化物和导电剂的复合材料 |
CN104609376A (zh) * | 2015-01-30 | 2015-05-13 | 浙江工业大学 | 一种硫化锂粉体的制备方法 |
CN108190845A (zh) * | 2018-01-31 | 2018-06-22 | 湖南省正源储能材料与器件研究所 | 一种制备硫化锂的方法 |
CN110790239B (zh) * | 2019-08-26 | 2022-01-28 | 浙江工业大学 | 一种硫化锂粉体的机械球磨合成方法 |
CN112678781B (zh) * | 2019-10-18 | 2022-04-15 | 天齐锂业(江苏)有限公司 | 硫化锂的制备方法 |
CN111517288A (zh) * | 2020-05-07 | 2020-08-11 | 天目湖先进储能技术研究院有限公司 | 一种合成硫化锂的方法 |
CN112520703B (zh) * | 2020-08-03 | 2022-07-22 | 浙江工业大学 | 一种硫化锂的绿色制备方法 |
CN112408437B (zh) * | 2020-11-19 | 2023-03-28 | 江西天新药业股份有限公司 | 锂盐的回收方法 |
KR20220079456A (ko) | 2020-12-04 | 2022-06-13 | 주식회사 레이크머티리얼즈 | 황화리튬의 제조방법 |
CN112551491B (zh) * | 2020-12-10 | 2022-04-08 | 天津大学 | 一种硫化锂的制备方法、硫化锂及其应用 |
CN112624061B (zh) * | 2020-12-31 | 2022-09-20 | 江西赣锋锂业股份有限公司 | 一种利用工业级丁基锂制备碳/硫化锂正极复合材料的方法 |
CN112624060B (zh) * | 2020-12-31 | 2022-09-20 | 江西赣锋锂业股份有限公司 | 一种利用工业级丁基锂制备高纯硫化锂的方法 |
CN113415812B (zh) * | 2021-06-23 | 2023-03-24 | 高能时代(珠海)新能源科技有限公司 | 一种高纯硫化锂的制备方法及应用 |
US20230150828A1 (en) | 2021-11-16 | 2023-05-18 | Solid Power Operating, Inc. | Lithium sulfide production method |
CN114455550B (zh) * | 2022-01-20 | 2023-07-18 | 湖北索立德新能源科技有限责任公司 | 硫化锂的制备方法 |
WO2023224150A1 (ko) * | 2022-05-20 | 2023-11-23 | 주식회사 솔리드아이오닉스 | 황화리튬 제조 방법 |
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- 2012-05-29 DE DE102012208982A patent/DE102012208982A1/de not_active Withdrawn
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- 2012-05-29 KR KR1020137034805A patent/KR101963297B1/ko active IP Right Grant
- 2012-05-29 CN CN201280025805.0A patent/CN103813980B/zh active Active
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JP2014518838A (ja) | 2014-08-07 |
US20140084224A1 (en) | 2014-03-27 |
KR101963297B1 (ko) | 2019-03-28 |
DE102012208982A1 (de) | 2012-11-29 |
KR20140053034A (ko) | 2014-05-07 |
EP2714587A2 (de) | 2014-04-09 |
WO2012163900A2 (de) | 2012-12-06 |
EP2714587B1 (de) | 2016-04-06 |
WO2012163900A3 (de) | 2013-05-30 |
JP6016899B2 (ja) | 2016-10-26 |
CN103813980A (zh) | 2014-05-21 |
US9017582B2 (en) | 2015-04-28 |
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