Ionic Conductivity of Nanocrystalline and Amorphous Li(10)GeP(2)S(12): The Detrimental Impact of Local Disorder on Ion Transport

[Image: see text] Solids with extraordinarily high Li(+) dynamics are key for high performance all-solid-state batteries. The thiophosphate Li(10)GeP(2)S(12) (LGPS) belongs to the best Li-ion conductors with an ionic conductivity exceeding 10 mS cm(–1) at ambient temperature. Recent molecular dynamics simulations performed by Dawson and Islam predict that the ionic conductivity of LGPS can be further enhanced by a factor of 3 if local disorder is introduced. As yet, no experimental evidence exists supporting this fascinating prediction. Here, we synthesized nanocrystalline LGPS by high-energy ball-milling and probed the Li(+) ion transport parameters. Broadband conductivity spectroscopy in combination with electric modulus measurements allowed us to precisely follow the changes in Li(+) dynamics. Surprisingly and against the behavior of other electrolytes, bulk ionic conductivity turned out to decrease with increasing milling time, finally leading to a reduction of σ(20°C) by a factor of 10. (31)P, (6)Li NMR, and X-ray diffraction showed that ball-milling forms a structurally heterogeneous sample with nm-sized LGPS crystallites and amorphous material. At −135 °C, electrical relaxation in the amorphous regions is by 2 to 3 orders of magnitude slower. Careful separation of the amorphous and (nano)crystalline contributions to overall ion transport revealed that in both regions, Li(+) ion dynamics is slowed down compared to untreated LGPS. Hence, introducing defects into the LGPS bulk structure via ball-milling has a negative impact on ionic transport. We postulate that such a kind of structural disorder is detrimental to fast ion transport in materials whose transport properties rely on crystallographically well-defined diffusion pathways.