材料科学
离子
离子电导率
电解质
扩散
化学物理
电导率
离子键合
相(物质)
快离子导体
替代(逻辑)
相变
物理化学
热力学
化学
电极
物理
有机化学
计算机科学
程序设计语言
作者
Fabián A. García Daza,Mauricio R. Bonilla,Anna Llordes,Javier Carrasco,Elena Akhmatskaya
标识
DOI:10.1021/acsami.8b17217
摘要
Garnet-structured Li7La3Zr2O12 is a promising solid electrolyte for next-generation solid-state Li batteries. However, sufficiently fast Li-ion mobility required for battery applications only emerges at high temperatures, upon a phase transition to cubic structure. A well-known strategy to stabilize the cubic phase at room temperature relies on aliovalent substitution; in particular, the substitution of Li+ by Al3+ and Ga3+ ions. Yet, despite having the same formal charge, Ga3+ substitution yields higher conductivities (10-3 S/cm) than Al3+ (10-4 S/cm). The reason of such difference in ionic conductivity remains a mystery. Here, we use molecular dynamic simulations and advanced sampling techniques to precisely unveil the atomistic origin of this phenomenon. Our results show that Li+ vacancies generated by Al3+ and Ga3+ substitution remain adjacent to Ga3+ and Al3+ ions, without contributing to the promotion of Li+ mobility. However, while Ga3+ ions tend to allow limited Li+ diffusion within their immediate surroundings, the less repulsive interactions associated with Al3+ ions lead to a complete blockage of neighboring Li+ diffusion paths. This effect is magnified at lower temperatures and explains the higher conductivities observed for Ga-substituted systems. Overall, this study provides a valuable insight into the fundamental ion transport mechanism in the bulk of Ga/Al-substituted Li7La3Zr2O12 and paves the way for rationalizing aliovalent substitution design strategies for enhancing ionic transport in these materials.
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