Tuning Ion Mobility in Lithium Argyrodite Solid Electrolytes via Entropy Engineering

The development of improved solid electrolytes (SEs) plays a crucial role in the advancement of bulk‐type solid‐state battery (SSB) technologies. Recently, multicomponent or high‐entropy SEs are gaining increased attention for their advantageous charge transport and (electro)chemical properties. However, a comprehensive understanding of how configurational entropy affects ionic conductivity is largely lacking. Herein we have investigated a series of multication‐substituted lithium argyrodites with the general formula Li6+x[M1aM2bM3cM4d]S5I, with M being P, Si, Ge, and Sb. Structure‐property relationships related to ion mobility were probed using a combination of diffraction techniques, solid‐state nuclear magnetic resonance spectroscopy, and charge‐transport measurements. We present, to the best of our knowledge, the first experimental evidence of a direct correlation between occupational disorder in the cationic host lattice and lithium transport. By controlling the configurational entropy through the composition, high bulk ionic conductivities up to 18 mS cm−1 at room temperature were achieved for optimized lithium argyrodite compositions. Our results indicate the possibility of improving ionic conductivity in ceramic ion conductors via entropy engineering, unlocking the compositional limitations for the design of advanced electrolytes and opening up new avenues in the field.