Exploring the Relationship Between Halide Substitution, Structural Disorder, and Lithium Distribution in Lithium Argyrodites (Li6–xPS5–xBr1+x)

锂(药物) 离子电导率 卤化物 化学 离子键合 中子衍射 对分布函数 快离子导体 晶体结构 材料科学 无机化学 电解质 结晶学 离子 物理化学 有机化学 数学分析 内分泌学 医学 数学 电极
作者
Ajay Kumar Gautam,Hanan Al-Kutubi,Theodosios Famprikis,Swapna Ganapathy,Marnix Wagemaker
出处
期刊:Chemistry of Materials [American Chemical Society]
卷期号:35 (19): 8081-8091 被引量:1
标识
DOI:10.1021/acs.chemmater.3c01525
摘要

Lithium argyrodite superionic conductors have recently gained significant attention as potential solid electrolytes for all-solid-state batteries because of their high ionic conductivity and ease of processing. Promising aspects of these materials are the ability to introduce halides (Li6-xPS5-xHal1+x, Hal = Cl and Br) into the crystal structure, which can greatly impact the lithium distribution over the wide range of accessible sites and the structural disorder between the S2- and Hal- anion on the Wyckoff 4d site, both of which strongly influence the ionic conductivity. However, the complex relationship among halide substitution, structural disorder, and lithium distribution is not fully understood, impeding optimal material design. In this study, we investigate the effect of bromide substitution on lithium argyrodite (Li6-xPS5-xBr1+x, in the range 0.0 ≤ x ≤ 0.5) and engineer structural disorder by changing the synthesis protocol. We reveal the correlation between the lithium substructure and ionic transport using neutron diffraction, solid-state nuclear magnetic resonance (NMR) spectroscopy, and electrochemical impedance spectroscopy. We find that a higher ionic conductivity is correlated with a lower average negative charge on the 4d site, located in the center of the Li+ "cage", as a result of the partial replacement of S2- by Br-. This leads to weaker interactions within the Li+ "cage", promoting Li-ion diffusivity across the unit cell. We also identify an additional T4 Li+ site, which enables an alternative jump route (T5-T4-T5) with a lower migration energy barrier. The resulting expansion of the Li+ cages and increased connections between cages lead to a maximum ionic conductivity of 8.55 mS/cm for quenched Li5.5PS4.5Br1.5 having the highest degree of structural disorder, an 11-fold improvement compared to slow-cooled Li6PS5Br having the lowest degree of structural disorder. Thereby, this work advances the understanding of the structure-transport correlations in lithium argyrodites, specifically how structural disorder and halide substitution impact the lithium substructure and transport properties and how this can be realized effectively through the synthesis method and tuning of the composition.
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