New crystal structure of Li3YCl6: structural relationship and ionic conductivity for solid-state electrolytes

IF 9.6 1区 材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY
Ji Hoon Kim, Byeongsun Jun, Yong Jun Jang, Chi Ho Lee, Sang Uck Lee
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Abstract

In the pursuit of safer and more energy-dense all-solid-state Li-ion batteries, solid-state electrolytes (SSEs) have emerged as pivotal components, with halide SSEs distinguished by their excellent electrochemical stability, enhanced Li-ion diffusion, and potential cost-efficiency. These properties depend on the anion elements and the structure of closely packed anion sublattices, such as cubic close-packed (ccp) and hexagonal close-packed (hcp) frameworks. Hence, understanding these key differences is essential because they influence the ion diffusion kinetic properties of various halide SSEs. However, research has predominantly shown that ccp anion sublattices generally exhibit higher ionic conductivities than their hcp counterparts, often overlooking the importance of the structural frameworks. To address this issue, we re-evaluated the assumption that a ccp framework is necessary for high electrochemical performance. Specifically, we utilized the three previously synthesized hcp and a ccp frameworks, all with an identical composition of Li3YCl6, to assess their thermodynamic stability, synthesizability, and ionic conductivity through ab initio molecular dynamics simulations. The results revealed that hcp frameworks could be promising candidates for SSEs, challenging the conventional preference for the ccp framework. With this structural insight, we designed a novel hcp framework to predict a new Li3YCl6 crystal structure with the highest ionic conductivity (38 mS·cm−1) among the halide frameworks and a superior 2D Li-ion diffusion pathway. This breakthrough underscores the significance of the anion framework geometry in Li-ion diffusion and highlights the importance of precise crystallographic predictions in developing more efficient and cost-effective battery technologies.

Graphical Abstract

Li3YCl6的新晶体结构:固态电解质的结构关系和离子电导率
在追求更安全、能量密度更高的全固态锂离子电池的过程中,固态电解质(sse)已成为关键部件,其中卤化物sse具有优异的电化学稳定性、增强的锂离子扩散能力和潜在的成本效益。这些性质取决于阴离子元素和紧密排列的阴离子亚晶格的结构,如立方紧密排列(ccp)和六边形紧密排列(hcp)框架。因此,了解这些关键的差异是必不可少的,因为它们会影响各种卤化物sse的离子扩散动力学特性。然而,研究主要表明,ccp阴离子亚晶格通常比它们的hcp对偶具有更高的离子电导率,往往忽视了结构框架的重要性。为了解决这个问题,我们重新评估了ccp框架是高电化学性能所必需的假设。具体来说,我们利用之前合成的三种hcp和ccp框架,都具有相同的Li3YCl6组成,通过从头算分子动力学模拟来评估它们的热力学稳定性、可合成性和离子电导率。结果表明,hcp框架可能是有希望的候选框架,挑战了传统的ccp框架偏好。利用这种结构洞察力,我们设计了一种新的hcp框架来预测具有最高离子电导率(38 mS·cm−1)的新型Li3YCl6晶体结构,并具有优越的二维锂离子扩散途径。这一突破强调了阴离子框架几何结构在锂离子扩散中的重要性,并强调了精确晶体学预测在开发更高效、更具成本效益的电池技术中的重要性。图形抽象
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来源期刊
Rare Metals
Rare Metals 工程技术-材料科学:综合
CiteScore
12.10
自引率
12.50%
发文量
2919
审稿时长
2.7 months
期刊介绍: Rare Metals is a monthly peer-reviewed journal published by the Nonferrous Metals Society of China. It serves as a platform for engineers and scientists to communicate and disseminate original research articles in the field of rare metals. The journal focuses on a wide range of topics including metallurgy, processing, and determination of rare metals. Additionally, it showcases the application of rare metals in advanced materials such as superconductors, semiconductors, composites, and ceramics.
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