Site preferences and ion dynamics in lithium chalcohalide solid solutions with argyrodite structure: I. A multinuclear solid state NMR study of the system Li6PS5-xSexI and of Li6AsS5I

Abstract

Abstract A comprehensive multinuclear (7Li, 31P, 75As, 77Se, 127I) NMR study has been conducted to characterize local structural configurations and atomic distributions in the crystallographically ordered solid solutions of composition Li6PS5-x Se x I (0 ≤ x ≤ 1) and in Li6AsS5I. Throughout the composition range, structural ordering between the atoms on the Wyckoff sites 4a and 4c is maintained, with the I− ions exclusively occupying the 4a sites. 31P magic-angle spinning nuclear magnetic resonance (MAS NMR) can serve to differentiate between the various possible PS4-n Se n 3− tetrahedral units in a quantitative fashion, indicating a preference of P-S relative to P-Se bonding. Each individual PS4-n Se n 3− tetrahedron is represented by a peak cluster containing up to five resonances, representing the five different configurations in which the PCh4 3− units are surrounded by the four closest chalcogenide anions occupying the 4c sites; the distribution of S2− and Se2− over these sites is close to statistical. Non-linear 7Li chemical shift trends as a function of x are interpreted to indicate that the Coulombic traps created by sulfur-rich PS4-n Se n 3− ions (n ≥ 2) within the energy landscape of the lithium ions are deeper than those of the other anionic species present (i.e. selenium-richer PCh4 3− tetrahedra, isolated chalcogenide or iodide ions), causing the Li+ ions to spend on average more time near them. Temperature dependent static 7Li NMR linewidths measured on Li6PS5I and Li6AsS5I indicate a two-step motional narrowing process characterized by a clear dynamic distinction between a more rapid localized intra-cage process and a slower, long-range inter-cage process. In the solid solutions this differentiation gradually disappears, leading to an overall increase of lithium ionic mobility with increasing selenium content, which can be attributed to the influences of higher anionic polarizability and a widening of the lithium migration pathways caused by lattice expansion. Furthermore, the low-temperature phase transition in Li6PS5I, which tends to immobilize the lithium ions below 170 K, is suppressed in the solid solutions. The results offer interesting new insights into the -structure/ionic mobility correlations in this new class of compounds.