Li 15 P 4 S 16 Cl 3 , a Lithium Chlorothiophosphate as a Solid-State Ionic Conductor
Li 15 P 4 S 16 Cl 3 , a Lithium Chlorothiophosphate as a Solid-State Ionic Conductor
复制标题
Li 15 P 4 S 16 Cl 3 ，一种固态离子导体氯硫代磷酸锂
DOI：
10.1021/acs.inorgchem.9b01751
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发表时间：
2019
影响因子：
4.6
通讯作者：
Chen, Hailong
中科院分区：
文献类型：
--
作者：
Liu, Zhantao;Zinkevich, Tatiana;Indris, Sylvio;He, Xingfeng;Liu, Jue;Xu, Wenqian;Bai, Jianming;Xiong, Shan;Mo, Yifei;Chen, Hailong
在固体Li+电解液的设计和全固态电池的开发方面付出了巨大的努力。与使用易燃液体有机电解液的传统锂离子电池相比，全固态电池在安全性方面显示出显著的优势。在本工作中，发现了一种新的氯代硫代磷酸锂化合物Li15P4S16Cl3。对其晶体结构和电化学性质进行了研究。通过简单的固相反应，在360℃加热Li2S、P2S5和LiCl3的球磨混合物，可以合成出纯的Li15P4S16Cl3。根据中子和同步辐射粉末的X射线衍射数据对Li15P4S16Cl3的晶体结构进行了修正，表明它在空间群I4̅3d中结晶。用变温核磁共振线形分析、核磁共振弛豫法和脉冲场梯度核磁共振等多种固体核磁共振方法研究了Li+在Li15P4S16Cl3中的输运过程。Li15P4S16Cl3具有良好的热力学稳定性，可以在较低的温度下合成。虽然它在室温下表现出较低的离子电导率，但它可以作为一种新的基元晶体结构，用于设计和开发新的固体电解质。
Tremendous efforts have been devoted to the design of solid Li+electrolytes and the development of all-solid-state batteries. Compared with conventional Li-ion batteries, which use flammable liquid organic electrolytes, all-solid-state batteries show significant advantages in safety. In this work, a novel lithium chlorothiophosphate compound, Li15P4S16Cl3, is discovered. The crystal structure and electrochemical properties are investigated. Li15P4S16Cl3can be synthesized as a pure phase via a facile solid-state reaction by heating a ball-milled mixture of Li2S, P2S5, and LiCl at 360 °C. The crystal structure of Li15P4S16Cl3was refined against neutron and synchrotron powder X-ray diffraction data, revealing that it crystallizes in the space groupI4̅3d. The Li+transport in Li15P4S16Cl3was also investigated by multiple solid-state NMR methods, including variable-temperature NMR line-shape analysis, NMR relaxometry, and pulsed-field-gradient NMR. Li15P4S16Cl3shows good thermodynamic stability and can be synthesized at relatively low temperature. Although it exhibits a low ionic conductivity at room temperature, it can serve as a new motif crystal structure for the design and development of new solid-state electrolytes.