In pursuit of developing efficient solid electrolytes for advanced battery technologies, significant research has been dedicated to thiophosphate-based materials. Among these, lithium argyrodites have emerged as a highly researched class, with promising conductive properties reaching up to 24 mS cm -1 . However, it is important to note that these materials often exhibit varying degrees of disorder, particularly in the form of anion exchange between halides and sulfur sites. This anion exchange phenomenon has a significant influence on the cationic transport properties, prompting numerous studies aimed at understanding the impact of iso-and aliovalent substitutions on this exchange process. Nevertheless, altering the chemical composition introduces complexities in comprehending the resultant transport properties, thereby making it challenging to isolate individual influences.