Grain boundary stability and influence on ionic conductivity in a disordered perovskite—a first-principles investigation of lithium lanthanum titanate

Alexander, Kathleen C.; Ganesh, Panchapakesan; Chi, Miaofang; Kent, Paul; Sumpter, Bobby G.

doi:10.1557/mrc.2016.58

Cited by 12 publications

(11 citation statements)

References 28 publications

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“…In recent years, although more and more powerful techniques are demonstrated as effective tools for the characterization of SCLs 4,18 , their atomic configurations remain unexplored. Therefore, despite the large number of insightful computational studies in recent years [19][20][21][22][23][24] , the absence of experimental verification still prevents the conclusive, precise comprehension of the critical interfaces involving SCLs.…”

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confidence: 99%

Atomic-scale study clarifying the role of space-charge layers in a Li-ion-conducting solid electrolyte

Zhu

et al. 2023

Nat Commun

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Space-charge layers are frequently believed responsible for the large resistance of different interfaces in all-solid-state Li batteries. However, such propositions are based on the presumed existence of a Li-deficient space-charge layer with insufficient charge carriers, instead of a comprehensive investigation on the atomic configuration and its ion transport behavior. Consequently, the real influence of space-charge layers remains elusive. Here, we clarify the role of space-charge layers in Li0.33La0.56TiO3, a prototype solid electrolyte with large grain-boundary resistance, through a combined experimental and computational study at the atomic scale. In contrast to previous speculations, we do not observe the Li-deficient space-charge layers commonly believed to result in large resistance. Instead, the actual space-charge layers are Li-excess; accommodating the additional Li+ at the 3c interstitials, such space-charge layers allow for rather efficient ion transport. With the space-charge layers excluded from the potential bottlenecks, we identify the Li-depleted grain-boundary cores as the major cause for the large grain-boundary resistance in Li0.33La0.56TiO3.

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confidence: 99%

Atomic-scale study clarifying the role of space-charge layers in a Li-ion-conducting solid electrolyte

Zhu

et al. 2023

Nat Commun

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“…3). 36 A-site deficient GB shows slightly higher grain boundary formation energy ( E GB = 0.882 J m −2 ) compared to the ∑3(111) grain boundary, but it is still fairly low compared to other perovskite materials, indicating that an A-site deficient GB is likely to appear in the real LLTO systems. For a comparative analysis with stoichiometric GBs, the local atomic structure at the GB core was investigated thoroughly.…”

Section: Resultsmentioning

confidence: 90%

First principles study on Li metallic phase nucleation at grain boundaries in a lithium lanthanum titanium oxide (LLTO) solid electrolyte

Conlin¹,

Bergschneider²,

Chung³

et al. 2023

J. Mater. Chem. A

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“…Further calculations based on the Nudged Elastic Band method revealed a lower formation energy of such grain boundaries and the traditional vacancy migration mechanism does not work. [77] Such atomic scale microscopy and theoretical studies not only allow for a mechanistic understanding of the GB resistance in SEs, but also point out potential grain boundary modifications that could deliver fast ion conduction.…”

Section: A U T H O R Accepted Manuscriptmentioning

confidence: 99%

Mechanistic understanding and strategies to design interfaces of solid electrolytes: insights gained from transmission electron microscopy

Hood

Chi

2019

J Mater Sci

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Solid electrolytes (SEs) have garnered increased attention for their promise to enable higher volumetric energy density and enhanced safety required for future battery systems. SEs are not only a key constituent in all-solid-state batteries, but also are important "protectors" of Li-metal anodes in next-generation battery configurations, such as Li-air, Li-S, redox flow batteries, among others. The impedance at interfaces associated with SEs, e.g. internal grain/phase boundaries and their interfacial stability with electrodes, represent two key factors limiting the performance of SEs, yet analyzing these interfaces experimentally at the nano/atomic scale is generally challenging. A mechanistic understanding of the possible instability at interfaces and propagation of interfacial resistance will pave the way to the design of high-performance SE-based batteries. In this review, we briefly introduce the fundamentals of SEs and challenges associated with their interfaces. Next, we discuss experimental techniques that allow for atomic-to-microscale understanding of ion transport and stability in SEs and at their interfaces, specifically highlighting the applications of state-of-art and emerging ex situ and in situ transmission electron microscopy (TEM) and scanning TEM (STEM). Representative examples from current literature that exemplify recent fundamental insights gained from these S/TEM techniques are highlighted. Applicable strategies to improve ion conduction and interfaces in SE-based batteries are also discussed. This review concludes by highlighting opportunities for future research that will significantly promote the fundamental understanding of SEs, specifically further developments in S/TEM techniques that will bring new insights into the design of high-performance interfaces for future electrical energy storage.

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Grain boundary stability and influence on ionic conductivity in a disordered perovskite—a first-principles investigation of lithium lanthanum titanate

Abstract: Abstract

Cited by 12 publications

References 28 publications

Atomic-scale study clarifying the role of space-charge layers in a Li-ion-conducting solid electrolyte

Atomic-scale study clarifying the role of space-charge layers in a Li-ion-conducting solid electrolyte

First principles study on Li metallic phase nucleation at grain boundaries in a lithium lanthanum titanium oxide (LLTO) solid electrolyte

Mechanistic understanding and strategies to design interfaces of solid electrolytes: insights gained from transmission electron microscopy

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