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Argyrodite sulfide solid electrolytes, such as Li6PS5Cl (LPSC), have received much attention due to their high ionic conductivity (1 mS cm-1) and success in all-solid-state batteries (long cycle performance, high energy density, etc.). Numerous efforts are spent on modifying the properties of the electrolyte itself. Here, we combine first-principles calculations with experiments to investigate O-doped argyrodite sulfide solid electrolytes (Li6PS5-xClOx, x = 0-1). It is found that Li6PS4.75ClO0.25 (LPSCO0.25) with x = 0.25 and cubic
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