揭示陶瓷固体电解质晶界缺锂的成因

IF 18.2 1区材料科学 Q1 CHEMISTRY, PHYSICAL

ACS Energy Letters Pub Date : 2025-03-24 DOI:10.1021/acsenergylett.5c00117

Xiaoming Liu, Zhengwu Fang, Yubin Zhang, Yan Wang, W. Beck Andrews, Katsuyo Thornton, Neil P. Dasgupta, Miaofang Chi

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引用次数: 0

摘要

实现低晶界电阻的固体电解质是推进全固态电池发展的关键。SEs中的高GB电阻通常归因于在这些边界处缺乏可移动离子；然而，这些缺陷在合成过程中何时以及如何形成仍不清楚。在这里，我们使用一种独特的原位扫描透射电子显微镜装置来指导固体电解质在退火过程中的结晶，从而在原子尺度上实时观察GB的形成，以Li0.33La0.56TiO3为模型SE。我们发现了一层厚度小于1.5 nm的超薄缺锂层，该层在结晶时出现在结晶前沿，并在两个相邻晶体融合形成GB时持续存在。我们对缺锂层的起源提出了两种假设，一种是基于热力学稳定，另一种是基于动力学约束。我们的结果为设计降低固体电解质中GB电阻的合成策略提供了指导。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Unraveling the Origin of Grain Boundary Lithium Deficiency in Ceramic Solid Electrolytes

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Unraveling the Origin of Grain Boundary Lithium Deficiency in Ceramic Solid Electrolytes

Realizing solid electrolytes with low grain-boundary (GB) resistance is critical for advancing all-solid-state batteries. High GB resistance in SEs is often attributed to deficiencies in mobile ions at these boundaries; yet, when and how these deficiencies form during synthesis remain unclear. Here, we use a unique in situ scanning transmission electron microscopy setup to guide solid electrolyte crystallization during annealing, enabling real-time observation of GB formation at the atomic scale, with Li_0.33La_0.56TiO₃ as a model SE. We reveal an ultrathin, less than 1.5 nm thick, lithium-deficient layer that emerges at the crystallization front upon crystallization and persists as two adjacent crystals fuse to form a GB. We offer two hypotheses for the origin of the lithium-deficient layer, one based on thermodynamic stabilization and the other on kinetic constraints. Our results provide guidelines for designing synthesis strategies to reduce GB resistance in solid electrolytes.

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来源期刊

ACS Energy Letters Energy-Renewable Energy, Sustainability and the Environment

CiteScore

31.20

自引率

5.00%

发文量

469

审稿时长

1 months

期刊介绍： ACS Energy Letters is a monthly journal that publishes papers reporting new scientific advances in energy research. The journal focuses on topics that are of interest to scientists working in the fundamental and applied sciences. Rapid publication is a central criterion for acceptance, and the journal is known for its quick publication times, with an average of 4-6 weeks from submission to web publication in As Soon As Publishable format. ACS Energy Letters is ranked as the number one journal in the Web of Science Electrochemistry category. It also ranks within the top 10 journals for Physical Chemistry, Energy & Fuels, and Nanoscience & Nanotechnology. The journal offers several types of articles, including Letters, Energy Express, Perspectives, Reviews, Editorials, Viewpoints and Energy Focus. Additionally, authors have the option to submit videos that summarize or support the information presented in a Perspective or Review article, which can be highlighted on the journal's website. ACS Energy Letters is abstracted and indexed in Chemical Abstracts Service/SciFinder, EBSCO-summon, PubMed, Web of Science, Scopus and Portico.