為了解決當今商用鋰離子電池的安全問題，使用固態電解質的固態鋰金屬電池被視為一種有效的解決方案。其中硫化物固態電解質Li6PS5Cl (LPSC)因具有良好的鋰離子導離度和延展性而受到廣泛關注。然而，LPSC在導離度及穩定性方面仍面臨相當大的挑戰。首先，LPSC的鋰離子導離度仍低於商用液態電解質，另外，LPSC在與水反應後會產生有毒氣體硫化氫。因此，本研究使用密度泛函理論 (DFT) 和第一原理分子動力學 (AIMD) 模擬，探討了LPSC中不同異價陽離子取代磷並考慮氯電荷平衡(去除氯)或鋰電荷平衡 (添加鋰) 的兩種方式，比較鋰離子導離度的差異。計算結果表明，在氯電荷平衡方面，Li6P0.75La0.25S5Cl0.5與 Li6P0.75Y0.25S5Cl0.5分別展現出比LPSC 高11倍 (2.608 mS cm-1) 及10倍 (2.337mS cm-1)的鋰離子導離度；而在鋰電荷平衡方面，Li6.25P0.75Ti0.25S5Cl 表現出最高的鋰離子導離度(5.510 mS cm-1)，為LPSC的23倍。另外，我們也透過DFT計算來探討LPSC和Ti-LPSC表面的水解反應機制。結果表明，Ti-LPSC在速率決定步驟上的能障比LPSC大，因而擁有了更佳的水氣穩定性。由上述結果可知，在LPSC上進行鈦原子取代並透過鋰離子進行電荷平衡，表現出比LPSC更高的鋰離子導離度與水氣穩定性，是個非常具有發展潛力的新型固態電解質材料。

The use of solid-state electrolytes (SSEs) in solid-state lithium metal batteries has been recognized as an effective solution for addressing the safety concerns associated with current commercially available lithium-ion batteries. Sulfide-based SSEs, specifically Li6PS5Cl (LPSC), have received considerable attention among the various SSE types available due to their excellent Li+ ionic conductivity and impressive flexibility. However, there are two major issues with LPSC should be addressed. First, the Li+ ionic conductivity of LPSC is lower than that of liquid electrolytes. Second, the moisture stability of LPSC is a concern because it reacts with water (H2O) and forms the toxic gas hydrogen sulfide (H2S). Therefore, this study uses density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations to explore the Li+ ionic conductivities of different aliovalent cations substituted for phosphorus on LPSC bulk. Here while substituting the aliovalent cations, the effects of charge balance by either removing chlorine (Cl-charge balance) or adding lithium atoms (Li-charge balance) on Li+ ionic conductivities are studied. The results show that the Li6P0.75La0.25S5Cl0.5 system has the highest Li+ ionic conductivity of 2.608 mS cm-1 in the Cl-charge balance, which is eleven times higher than the pristine LPSC. Li6P0.75Y0.25S5Cl0.5 also has a high Li+ ionic conductivity of 2.337 mS cm-1, which is ten times greater than pristine LPSC. In terms of Li-charge balance, Li6.25P0.75Ti0.25S5Cl demonstrates the highest Li+ ionic conductivity of 5.510 mS cm-1, which is twenty-three times greater than the pristine LPSC. Furthermore, DFT calculations were employed to investigate the hydrolysis reaction mechanism of both pristine LPSC and Ti-LPSC surfaces. The results revealed that after doping with titanium atoms, the activation barrier of the rate-determining step is higher compared to pristine LPSC, thereby enhancing the moisture stability of the material. Based on these theoretical results, it is found that the Li-Charge balance with the titanium atom substitution on LPSC has not only high Li+ ionic conductivity but also improved moisture stability than pristine LPSC.

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