近年來，全固態電解質因其安全性和能量密度高於應用在鋰離子電池中的傳統液態電解質而得到廣泛的研究。在眾多固態電解質中，硫化物基固態電解質因其具有與液態電解質相當的離子電導率，以及比其他氧化物基石榴石型和 NaSICON 型固態電解質有更好的延展性而受到關注。然而，硫化物基固態電解質的高濕度敏感特性，在接觸水氣時會產生有毒的硫化氫氣體，使其合成具有挑戰性且應用受到了限制。
在此，我們以Cl-取代S2-、Si4+取代P5+，並藉由機械球磨和固態燒結製備而成，利用同步加速器的原位XRD研究燒結溫度對結晶度及雜相的影響，進一步優化燒結條件，開發一系列雙摻雜於硫銀鍺礦之硫化物固態電解質(Li6PS5Cl，LPSC)：Li6-xPS5-xCl1+x、Li6+yP1-ySiyS5Cl、Li6.1-xP0.9Si0.1S5-xCl1+x、Li6.2-xP0.8Si0.2S5-xCl1+x (0≦x≦0.8, 0≦y≦0.5)，此外，以液態氮快速降溫證明可以保留固態電解質在高溫下的晶相。該系列之晶體結構、離子電導率和物理性質等藉由X射線粉末衍射(XRD)、拉曼光譜、阻抗測量及空氣穩定性測試進行表徵，並藉由鋰對稱電池及循環伏安法分析材料之電化學性能。氯摻雜固態電解質中以Li5.4PS4.4Cl1.6為最佳摻雜比，其離子電導率可以達到7.59 mS cm-1；矽摻雜之固態電解質中以 Li6.2P0.8Si0.2S5Cl為最佳摻雜比，可以達到2.2 mS cm-1，而氯與矽雙摻雜之固態電解質中以Li5.6P0.9Si0.1S4.5Cl1.5為最佳摻雜比，可以達到3.34 mS cm-1，為未摻雜LPSC參考樣品(1.8 mS cm-1)的1.8倍。這項研究表明，藉由陰離子取代增加位點無序性與異價陽離子取代促進鋰離子擴散，達到提升離子電導率之效果。此外，通過矽的取代，使Li5.6P0.9Si0.1S4.5Cl1.5之水氣穩定性大幅提升。在SSEs-VGCF｜SSEs｜Li-In半電池系統中，表現出良好的化學穩定性，且於鋰對稱電池測試中，在0.1 mA cm-2之電流密度下Li5.6P0.9Si0.1S4.5Cl1.5具有出色的循環穩定性及抑制鋰枝晶能力，且可承受最大電流密度為2.5 mA cm-2，顯示出相對小且穩定的極化現象。以氯及矽摻雜之硫銀鍺礦是一種兼有高穩定性及離子電導率的新型硫化物固態電解質，適合應用於全固態鋰金屬電池中。

All-solid-state electrolytes (SSEs) have been extensively investigated recently due to their superior safety and higher energy density than conventional liquid-based electrolytes for lithium-ion batteries (LIBs). Among various SSEs, sulfide-based all-solid-state lithium batteries (ASSLBs) have gained significant attention because of their comparable ionic conductivity to liquid electrolytes and better ductility than other oxide-based garnet-type and NaSICON-type SSEs. However, sulfide-based SSEs’ high moisture affinity is prone to producing toxic H2S gas when subject to humidity, making it challenging to handle and synthesize.
To develop a stabler Li-argyrodite electrolyte (Li6PS5Cl, LPSC), Cl- anion was selected to substitute S2- and aliovalent Si4+ cation for P5+, prepared by mechanical milling and solid-state sintering. The sintering conditions have been optimized with the synchrotron-based in-situ XRD to investigate the effect of sintering temperature on the crystallinity and impurities. A series of dual-doped solid-state electrolytes have been developed and analyzed, e.g., Li6-xPS5-xCl1+x, Li6+yP1-ySiyS5Cl, Li6.1-xP0.9Si0.1S5-xCl1+x, Li6.2-xP0.8Si0.2S5-xCl1+x (0≦x≦0.8, 0≦y≦0.5), In addition, a quenching method was also employed to retain the crystalline phase of SSE at high temperatures. The crystalline, chemical structure, ionic conductivity, and physical properties of the as-prepared samples were characterized by X-ray powder diffraction (XRD), Raman spectroscopy, impedance measurement, and air stability test. The electrochemical performance was characterized by a lithium symmetric battery and cyclic voltammetry. The optimal doping ratio of Li5.4PS4.4Cl1.6 in chlorine-doped argyrodite exhibited a high ionic conductivity of 7.6 mS cm-1. Among the silicon-doped argyrodite, Li6.2P0.8Si0.2S5Cl showed an ionic conductivity of 2.2 mS cm-1. The optimal doping ratio of Li5.6P0.9Si0.1S4.5Cl1.5 resulted in the highest ionic conductivity of 3.3 mS cm-1 at room temperature, 1.8 times higher than that of the reference, the pristine Li6PS5Cl (1.8 mS/cm). This work provides new insights into developing high ionic conductivity sulfide-based SSEs by highly substituting sulfur with chlorine anion and partially substituting phosphorus with the aliovalent silicon cation. Furthermore, the moisture stability of Li5.6P0.9Si0.1S4.5Cl1.5 was greatly improved by the dual dopants. In a SSEs-VGCF｜SSEs｜Li-In half-cell system, dual-doped Li6.2P0.8Si0.2S5Cl showed good chemical stability. In a lithium symmetric cell run at 0.1 mA cm-2, Li5.6P0.9Si0.1S4.5Cl1.5 demonstrated excellent compatibility with Li metal and achieved a critical current density as high as 2.5 mA cm-2. The argyrodite doped with chloride and silicon ion reveals itself as a new class of sulfide solid-state electrolyte with high stability and ionic conductivity, and the progress shows substantial promise for practical application in all-solid-state lithium batteries.

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