Synthesis, Structural Characterization, and Lithium Ion Conductivity of the Lithium Thiophosphate Li₂P₂S₆

Inspired by the ongoing search for new superionic lithium thiophosphates for use in solid-state batteries, we present the synthesis and structural characterization of Li 2 P 2 S 6, a novel crystalline lithium thiophosphate. Whereas M 2 P 2 S 6 with the different alkaline elements (M = Na, K, Rb, Cs) is known, the lithium counterpart has not been reported yet. Herein, we present a combination of synchrotron pair distribution function analysis and neutron powder diffraction to elucidate the crystal structure and possible Li + diffusion pathways of Li 2 P 2 S 6 . Additionally, impedance spectroscopy is used to evaluate its ionic conductivity. We show that Li 2 P 2 S 6 possesses P 2 S 6 2– polyhedral units with edge-sharing PS 4 tetrahedra and only one-dimensional diffusion pathways with localized Li–Li pairs, leading to a low ionic conductivity for lithium.