全固態電池（ASSLB）目前被認為是當前鋰離子電池技術的未來方向之一，因為它們具有更高的理論能量密度和更高的安全性。在ASSLB之中重要的組成是固態電解質（SE），其條件高離子傳導率和熱穩定性。在各種固態電解質中，硫銀鍺礦一直備受關注。在此，我們報告了一系列雙摻雜的固態電解質：Li6-2yFeyPS5Cl、Li6-x-2yFeyPS5-xCl1+x、Li6-x-2yFeyPS5-xClBrx。合成方法為透過固態燒結製備而成的。該系列的晶體結構、離子傳導率和物理性質通過X射線粉末衍射(XRD)、拉曼光譜、SEM、阻抗測量和空氣穩定性測試來進行表徵。
鐵單摻雜的固態電解質Li6-2yFeyPS5Cl導離度從1.28 mS/cm（Li6PS5Cl）提升至1.73 mS/cm（Li5.7Fe0.15PS5Cl），導離率提升的主要貢獻原因為在Li位點逐步引入Fe，使得鋰空位的逐漸增加。在鐵與氯的雙摻雜Li5.8-xFe0.1PS5-xCl1+x與Li5.7-xFe0.15PS5-xCl1+x之中，10%鐵的摻雜系列Li5.8-xFe0.1PS5-xCl1+x的導離度皆高於15%鐵的摻雜系列Li5.7-xFe0.15PS5-xCl1+x，原因為富含鹵素的硫銀鍺礦不能維持如此高的Fe取代度，會產生雜質，在這之中導離度以Li5.6Fe0.1PS4.8Cl1.2最高2.0 mS/cm。而在Li6-x-2yFeyPS5-xClBrx系列之中以Li5.5Fe0.1PS4.7ClBr0.3電解質在室溫下表現出最高的導離率2.1 mS/cm，幾乎為Li6PS5Cl導離度的一倍之高。導離度增加的原因為：鹵素的增加會產生鋰空缺，同時也增加了位點無序。此外，鋰離子和周圍骨架陰離子之間的靜電相互作用減弱，因此使得電解質的離子傳導率提升。此外，鐵的單摻雜以及鐵與鹵素的雙摻雜皆抑制了固態電解質接觸到水氣後產生的H2S氣體，以Li5.5Fe0.1PS4.7ClBr0.3的H2S產生量最低，為Li6PS5Cl產量的一半。而鋰對稱電池的結果顯示介面的不穩定性，若要應用於全固態電池中還有需要改值的地方。整體而言，透過鐵與鹵素的取代以增加鋰空缺，可增加硫銀鍺礦的導離度，從而使硫銀鍺礦成為更理想的固態電解質。

All-solid-state lithium batteries (ASSLB) are currently considered future candidates for next-generation battery systems because of their higher theoretical energy density and higher safety. An important component in ASSLB is the solid electrolytes (SEs), which have high ionic conductivity and higher thermal stability. Among various solid electrolytes, argyrodites have been considered a promising SE for ASSLB. Here, we report a series of dual-doped solid electrolytes: Li6-2yFeyPS5Cl, Li6-x-2yFeyPS5-xCl1+x, Li6-x-2yFeyPS5-xClBrx, prepared by direct solid-state sintering. Their crystal structure, ion conductivity, and physical properties were characterized by X-ray powder diffraction (XRD), Raman spectroscopy, SEM, impedance measurement, and air stability test.
The ionic conductivity of iron-doped solid electrolyte Li6-2yFeyPS5Cl increased from 1.28 mS/cm (Li6PS5Cl) to 1.73 mS/cm (Li5.7Fe0.15PS5Cl). The step-wise introduction of Fe in Li sites causes the gradual increase in lithium vacancies. The ionic conductivity of 10% iron-doped series Li5.8-xFe0.1PS5-xCl1+x is higher than 15% Fe doped series Li5.7-xFe0.15PS5-xCl1+x. The halogen-rich argyrodite cannot maintain such a high degree as the Fe dopant and causes impurities. Among the iron and chloride dual-doped materials, Li5.6Fe0.1PS4.8Cl1.2 shows the highest ionic conductivity of 2.0 mS/cm. For the iron and bromide dual-doped Li6-x-2yFeyPS5-xClBrx series, Li5.5Fe0.1PS4.7ClBr0.3 exhibits the highest ionic conductivity of 2.1 mS/cm, which is almost twice as high as that of Li6PS5Cl. The enhanced ionic conductivity results from the increase in lithium vacancies and site disorder caused by halide substitution. In addition, this modification of anions decreases in Li+ attraction to anion framework.
Both of the introduction of iron and halide can suppress the H2S gas generation from the solid electrolyte, when exposed to moisture. The H2S generated from Li5.5Fe0.1PS4.7ClBr0.3 is the lowest, which is almost half of Li6PS5Cl. However, the results from the Li symmetric cell show unstable interface toward lithium metal. Thus, further improvement of the electrolyte will be needed for the application in ASSLB. This work showㄋ that the substitution of iron and halide can increase the lithium vacancy and optimize the argyrodite's ionic conductivity, thereby making them an ideal solid electrolyte in ASSLB.

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