Jihun Roh, Hyojin Kim, Hyungjin Lee, Hyeri Bu, Alicia Manjón-Sanz, Hyungsub Kim, Seung-Tae Hong
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引用次数: 0
Abstract
Safety concerns regarding organic-based liquid electrolytes in Li-ion batteries have led to extensive research on lithium-ion conductors. Despite cost-effectiveness, thio-silicate Li4SiS4 has been overlooked owing to unclear crystallographic information. This study clarifies the crystal structures and electrochemical properties of two Li4SiS4 polymorphs and their aliovalent substitution series, i.e., Li4–xSi1–xSbxS4. Our findings indicate that the polymorphs differ primarily in their SiS4 tetrahedra stacking configurations, with the high-temperature phase being more orderly than the low-temperature phase. However, they exhibit similar ionic-transport properties, indicating that the tetrahedra stacking minimally affects Li-ion mobility. We found that the dense packing of Li in these structures restricts ion movement, necessitating the creation of Li vacancies through the aliovalent substitution of Sb5+ for Si4+ to enhance Li mobility. The substitution series Li4–xSi1–xSbxS4 with x = 0.15 exhibited a 10-fold conductivity increase, signifying the influence of Li vacancies on ionic transport. Cyclic voltammetry confirmed the suitability of Li3.85Si0.85Sb0.15S4 as a solid electrolyte for all-solid-state batteries. This study suggests that the ionic conductivity in Li4SiS4 depends more on Li-ion concentration than on SiS4 tetrahedra stacking, providing strategic insights for developing more efficient solid-state battery materials.
期刊介绍:
The journal Chemistry of Materials focuses on publishing original research at the intersection of materials science and chemistry. The studies published in the journal involve chemistry as a prominent component and explore topics such as the design, synthesis, characterization, processing, understanding, and application of functional or potentially functional materials. The journal covers various areas of interest, including inorganic and organic solid-state chemistry, nanomaterials, biomaterials, thin films and polymers, and composite/hybrid materials. The journal particularly seeks papers that highlight the creation or development of innovative materials with novel optical, electrical, magnetic, catalytic, or mechanical properties. It is essential that manuscripts on these topics have a primary focus on the chemistry of materials and represent a significant advancement compared to prior research. Before external reviews are sought, submitted manuscripts undergo a review process by a minimum of two editors to ensure their appropriateness for the journal and the presence of sufficient evidence of a significant advance that will be of broad interest to the materials chemistry community.