Disentangling Phase and Morphological Evolution During the Formation of the Lithium Superionic Conductor Li₁₀GeP₂S₁₂

Abstract The structural and morphological changes of the Lithium superionic conductor Li₁₀GeP₂S₁₂, prepared via a widely used ball milling‐heating method over a comprehensive heat treatment range (50 – 700 °C), are investigated. Based on the phase composition, the formation process can be distinctly separated into four zones: Educt, Intermediary, Formation, and Decomposition zone. It is found that instead of Li₄GeS₄–Li₃PS₄ binary crystallization process, diversified intermediate phases, including GeS₂ in different space groups, multiphasic lithium phosphosulfides (Li_xP_yS_z), and cubic Li₇Ge₃PS₁₂ phase, are involved additionally during the formation and decomposition of Li₁₀GeP₂S₁₂. Furthermore, the phase composition at temperatures around the transition temperatures of different formation zones shows a significant deviation. At 600 °C, Li₁₀GeP₂S₁₂ is fully crystalline, while the sample decomposed to complex phases at 650 °C with 30 wt.% impurities, including 20 wt.% amorphous phases. These findings over such a wide temperature range are first reported and may help provide previously lacking insights into the formation and crystallinity control of Li₁₀GeP₂S₁₂.