Correlation of Structure and Fast Ion Conductivity in the Solid Solution Series Li_1+2xZn_1–xPS₄

Solid electrolytes are the foundation of all-solid-state batteries (ASSB) and have the potential to provide improved safety and higher energy density than existing liquid battery systems. In the important search for new lithium ion conductors with fast ionic conductivity and good mechanical properties, thiophosphates are a particularly promising class of materials. The first experimental elucidation of new lithium ion conductors in the Li1+2xZn1-xPS4 (LZPS) solid solution whose existence had been predicted by theory is reported herein. Using neutron and synchrotron x-ray powder diffraction together with electrical impedance, and Raman studies, we resolve their crystalline nature and correlate this with ionic conductivity upon increasing the lithium/zinc ratio. We show that the materials exhibit high experimental ionic conductivities - up to 8 × 10-4 S·cm-1 - and reveal the nature of likely pathways for lithium ion conduction.