Domain boundaries and their influence on Li migration in solid-state electrolyte (La,Li)TiO3

Moriwake, Hiroki; Gao, Xiang; Kuwabara, Akihide; Fisher, Craig A. J.; Kimura, Teiichi; Ikuhara, Y.; Kohama, Keiichi; Tojigamori, Takeshi; Ikuhara, Yuichi

doi:10.1016/j.jpowsour.2014.11.139

Cited by 78 publications

(65 citation statements)

References 32 publications

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Section: Imagingmentioning

confidence: 99%

Advanced Transmission Electron Microscopy for Electrode and Solid‐Electrolyte Materials in Lithium‐Ion Batteries

Liu

2018

Small Methods

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Understanding the reaction processes of electrode and electrolyte materials is important for achieving high‐performance lithium‐ion batteries (LIBs). Currently, transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM) can readily characterize the structural and chemical features of these materials from the micrometer scale to the atomic scale. In situ (S)TEM can further monitor their non‐ or quasi‐equilibrated states in real time. Here, the recent progress in unraveling the crystal and electronic structures of the electrode and solid‐electrolyte materials using ex situ and in situ (S)TEM is reviewed. Three fundamental functions, including imaging, diffraction, and spectroscopy, are jointly used to decipher the configuration of the defects and ordering, the variations near the surfaces and across the interfaces, and the evolution of the coexisting phases. Novel and deep insights are proposed for the material growth, reaction, and capacity fading mechanisms. Advanced (S)TEM studies for LIB materials pose numerous challenges and perspectives, including the development and application of local diffraction analysis, large‐scale phase mapping techniques, 3D reconstruction, and cryoelectron microscopy, which are further discussed.

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Section: Imagingmentioning

confidence: 99%

Advanced Transmission Electron Microscopy for Electrode and Solid‐Electrolyte Materials in Lithium‐Ion Batteries

Liu

2018

Small Methods

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“…39,40 The higher concentration of A-site vacancies in LLNO than in LLTO (to maintain charge balance with the higher charge Nb 5+ cation compared with Ti 4+ ) would normally be expected to favour higher Li-ion mobility and hence higher ionic conductivity. 39,40 The higher concentration of A-site vacancies in LLNO than in LLTO (to maintain charge balance with the higher charge Nb 5+ cation compared with Ti 4+ ) would normally be expected to favour higher Li-ion mobility and hence higher ionic conductivity.…”

Section: Cation Ordering and Li-ion Pathways/mobilitymentioning

confidence: 99%

Cation ordering in A-site-deficient Li-ion conducting perovskites La_(1−x)/3Li_xNbO₃

et al. 2015

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Cation-deficient perovskites exhibit complex local atomic arrangements which cannot be adequately described by average crystal structure models. By combining reciprocal-space electron diffraction analysis and direct observations of atom positions using state-of-the-art scanning transmission electron microscopy, we clarify the nature of the cation ordering within A-site-deficient perovskite single crystals of La (1Àx)/3 Li x NbO 3 (x ¼ 0 and x ¼ 0.04). Both materials are found to have complex modulated crystal structures with two types of A-cation ordering, namely a long-range layer ordering in alternate (001) p planes and a short-range (intra-domain) columnar ordering within La-rich (001) p layers. The columnar ordering (occupational modulation) produces modulated displacements of Nb and O atoms. It is also found that substitution of even a small amount of Li for La can affect significantly the columnar ordering, leading to a series of structural and microstructural changes that are likely to have a deleterious effect on the Li-ion conductivity of this material.

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“…However, the two-dimensional lithium ion paths in this material are interrupted by grain boundaries, resulting in a high Rgb with σgrain boundary ≈ σtotal = 2 × 10 −5 Scm −1 (Inaguma et al, 1993;Stramare et al, 2003; et al, 2005;Gao et al, 2014;Moriwake et al, 2015). In contrast, the grain boundary resistance of garnet-like oxides is relatively low compared to other ion-conducting oxides because of the good lithium ion connection between grains, forming three dimensional lithium ion paths.…”

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confidence: 91%

Grain Boundary Analysis of the Garnet-Like Oxides Li7+X−YLa3−XAXZr2−YNbYO12 (A = Sr or Ca)

2016

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Garnet-like oxides having the formula Li7+X−YLa3−XAXZr2−YNbYO12 (A = Sr or Ca) were synthesized using a solid-state reaction, and their bulk and grain boundary resistivities were assessed by AC impedance measurements. A difference in grain boundary resistivity was identified between Sr and Ca materials, and so the grain boundaries were examined using electron probe microanalysis (EPMA). The difference in the grain boundary resistivities was attributed to the core-shell structure of the Sr-substituted samples. In contrast, the Ca-substituted materials exhibited accumulations of impurities at the grain boundaries.

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Domain boundaries and their influence on Li migration in solid-state electrolyte (La,Li)TiO3

Cited by 78 publications

References 32 publications

Advanced Transmission Electron Microscopy for Electrode and Solid‐Electrolyte Materials in Lithium‐Ion Batteries

Advanced Transmission Electron Microscopy for Electrode and Solid‐Electrolyte Materials in Lithium‐Ion Batteries

Cation ordering in A-site-deficient Li-ion conducting perovskites La_(1−x)/3Li_xNbO₃

Grain Boundary Analysis of the Garnet-Like Oxides Li7+X−YLa3−XAXZr2−YNbYO12 (A = Sr or Ca)

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Domain boundaries and their influence on Li migration in solid-state electrolyte (La,Li)TiO3

Cited by 78 publications

References 32 publications

Advanced Transmission Electron Microscopy for Electrode and Solid‐Electrolyte Materials in Lithium‐Ion Batteries

Advanced Transmission Electron Microscopy for Electrode and Solid‐Electrolyte Materials in Lithium‐Ion Batteries

Cation ordering in A-site-deficient Li-ion conducting perovskites La(1−x)/3LixNbO3

Grain Boundary Analysis of the Garnet-Like Oxides Li7+X−YLa3−XAXZr2−YNbYO12 (A = Sr or Ca)

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Cation ordering in A-site-deficient Li-ion conducting perovskites La_(1−x)/3Li_xNbO₃