Filling the Gaps in the LiBr-LiOH Phase Diagram: A Study on the High-Temperature Li3(OH)2Br Phase

IF 7 2区材料科学 Q2 CHEMISTRY, PHYSICAL

Chemistry of Materials Pub Date : 2025-04-03 DOI:10.1021/acs.chemmater.5c0020610.1021/acs.chemmater.5c00206

Emily Milan, James A. Quirk, Kenjiro Hashi, John Cattermull, Andrew L. Goodwin, James A. Dawson and Mauro Pasta*,

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Abstract

In this paper, we build on previous work to characterize a phase with stoichiometry Li₃(OH)₂Br existing between ∼225 and ∼275 °C in the LiBr-LiOH phase diagram. Diffraction studies indicate that the phase takes a hexagonal unit cell, and theoretical modeling is used to suggest a possible crystal structure. Nuclear magnetic resonance spectroscopy and electrochemical impedance spectroscopy measurements demonstrate excellent lithium-ion dynamics in this phase, with an ionic conductivity of 0.12 S cm^–1 at 250 °C. Initial attempts to stabilize this phase at room temperature through quenching were not successful. Instead, a metastable state demonstrating poor ionic conductivity is found to form. This is an important consideration for the synthesis of Li₂OHBr solid-state electrolytes (also found in the LiBr-LiOH phase diagram) which are synthesized by cooling through phase fields containing Li₃(OH)₂Br, and are hence susceptible to these impurities.

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填补LiBr-LiOH相图空白：高温Li3(OH)2Br相的研究

在本文中，我们在先前工作的基础上，对 LiBr-LiOH 相图中存在于 ∼225 °C和 ∼275 °C之间的化学计量为 Li3(OH)2Br 的相进行了表征。衍射研究表明，该相具有六边形单胞，并通过理论建模提出了可能的晶体结构。核磁共振波谱和电化学阻抗波谱测量结果表明，该相具有出色的锂离子动力学特性，在 250 °C 时离子电导率为 0.12 S cm-1。最初尝试通过淬火将这一相稳定在室温下，但没有成功。相反，发现形成了一种离子传导性较差的蜕变态。这对于合成 Li2OHBr 固态电解质（也出现在 LiBr-LiOH 相图中）来说是一个重要的考虑因素，这种电解质是通过含有 Li3(OH)2Br 的相场冷却合成的，因此很容易受到这些杂质的影响。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Chemistry of Materials 工程技术-材料科学：综合

CiteScore

14.10

自引率

5.80%

发文量

929

审稿时长

1.5 months

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.