posted on 2020-03-18, 20:03authored byRoman Schlem, Tim Bernges, Cheng Li, Marvin A. Kraft, Nicolo Minafra, Wolfgang G. Zeier
Driven
by the increasing attention that the superionic conductors
Li3MX6 (M = Y, Er, In, La; X = Cl, Br, I) have
gained recently for the use of solid-state batteries, and the idea
that a softer, more polarizable anion sublattice is beneficial for
ionic transport, here we report Li3ErI6, the
first experimentally obtained iodine-based compound within this material
system of ionic conductors. Using a combination of synchrotron and
neutron diffraction, we elucidate the structure, the lithium positions,
and possible diffusion pathways of Li3ErI6.
Temperature-dependent impedance spectroscopy shows low activation
energies of 0.37 and 0.38 eV alongside promising ionic conductivities
of 0.65 and 0.39 mS·cm–1 directly after ball
milling and the subsequently annealed Li3ErI6, respectively. Speed of sound measurements are used to determine
the Debye frequency of the lattice as a descriptor of the lattice
dynamics and overall lattice softness, and Li3ErI6 is compared to the known material Li3ErCl6. The softer, more polarizable framework from the iodide anion leads
to improved ionic transport, showing that the idea of softer lattices
holds up in this class of materials. This work provides Li3ErI6 as an interesting framework for optimization in the
class of halide-based ionic conductors.