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Li15P4S16Cl3, a Lithium Chlorothiophosphate as a Solid-State Ionic Conductor
journal contribution
posted on 2019-12-12, 18:37 authored by Zhantao Liu, Tatiana Zinkevich, Sylvio Indris, Xingfeng He, Jue Liu, Wenqian Xu, Jianming Bai, Shan Xiong, Yifei Mo, Hailong ChenTremendous 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.
Li15P4S16Cl3 can 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 Li15P4S16Cl3 was refined against neutron and synchrotron
powder X-ray diffraction data, revealing that it crystallizes in the
space group I4̅3d. The Li+ transport in Li15P4S16Cl3 was also investigated by multiple solid-state NMR methods,
including variable-temperature NMR line-shape analysis, NMR relaxometry,
and pulsed-field-gradient NMR. Li15P4S16Cl3 shows 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.