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Structural characterization of an amorphous VS(4) and its lithiation/delithiation behavior studied by solid-state NMR spectroscopy

Vanadium sulfide (VS(4)) is one of the promising positive electrode materials for next-generation rechargeable lithium-ion batteries because of its high theoretical capacity (1196 mA h g(−1)). Crystalline VS(4) has a unique structure, in which the Peierls-distorted one-dimensional chains of V–V bond...

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Autores principales: Shimoda, Keiji, Koganei, Kazuto, Takeuchi, Tomonari, Matsunaga, Toshiyuki, Murakami, Miwa, Sakaebe, Hikari, Kobayashi, Hironori, Matsubara, Eiichiro
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2019
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9069526/
https://www.ncbi.nlm.nih.gov/pubmed/35530591
http://dx.doi.org/10.1039/c9ra04338a
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author Shimoda, Keiji
Koganei, Kazuto
Takeuchi, Tomonari
Matsunaga, Toshiyuki
Murakami, Miwa
Sakaebe, Hikari
Kobayashi, Hironori
Matsubara, Eiichiro
author_facet Shimoda, Keiji
Koganei, Kazuto
Takeuchi, Tomonari
Matsunaga, Toshiyuki
Murakami, Miwa
Sakaebe, Hikari
Kobayashi, Hironori
Matsubara, Eiichiro
author_sort Shimoda, Keiji
collection PubMed
description Vanadium sulfide (VS(4)) is one of the promising positive electrode materials for next-generation rechargeable lithium-ion batteries because of its high theoretical capacity (1196 mA h g(−1)). Crystalline VS(4) has a unique structure, in which the Peierls-distorted one-dimensional chains of V–V bonds along the c axis are loosely connected to each other through van der Waals interactions. In this study, an amorphous VS(4) is prepared by mechanical milling of the crystalline material, and its lithiation/delithiation behavior is investigated by solid-state nuclear magnetic resonance (NMR) spectroscopy. The amorphous VS(4) shows a chain structure similar to that of crystalline VS(4). The amorphous host structure is found to change drastically during the lithiation process to form Li(3)VS(4): the V ions become tetrahedrally coordinated by S ions, in which the valence states of V and S ions simultaneously change from V(4+) to V(5+) and S(−) to S(2−), respectively. When the Li insertion proceeds further, the valence state of V ions is reduced. After the 1(st) cycle, the amorphous VS(4) recovers to the chain-like structure although it is highly disordered. No conversion to elemental V is observed, and a high capacity of 700 mA h g(−1) is reversibly delivered between 1.5 and 2.6 V.
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spelling pubmed-90695262022-05-05 Structural characterization of an amorphous VS(4) and its lithiation/delithiation behavior studied by solid-state NMR spectroscopy Shimoda, Keiji Koganei, Kazuto Takeuchi, Tomonari Matsunaga, Toshiyuki Murakami, Miwa Sakaebe, Hikari Kobayashi, Hironori Matsubara, Eiichiro RSC Adv Chemistry Vanadium sulfide (VS(4)) is one of the promising positive electrode materials for next-generation rechargeable lithium-ion batteries because of its high theoretical capacity (1196 mA h g(−1)). Crystalline VS(4) has a unique structure, in which the Peierls-distorted one-dimensional chains of V–V bonds along the c axis are loosely connected to each other through van der Waals interactions. In this study, an amorphous VS(4) is prepared by mechanical milling of the crystalline material, and its lithiation/delithiation behavior is investigated by solid-state nuclear magnetic resonance (NMR) spectroscopy. The amorphous VS(4) shows a chain structure similar to that of crystalline VS(4). The amorphous host structure is found to change drastically during the lithiation process to form Li(3)VS(4): the V ions become tetrahedrally coordinated by S ions, in which the valence states of V and S ions simultaneously change from V(4+) to V(5+) and S(−) to S(2−), respectively. When the Li insertion proceeds further, the valence state of V ions is reduced. After the 1(st) cycle, the amorphous VS(4) recovers to the chain-like structure although it is highly disordered. No conversion to elemental V is observed, and a high capacity of 700 mA h g(−1) is reversibly delivered between 1.5 and 2.6 V. The Royal Society of Chemistry 2019-08-05 /pmc/articles/PMC9069526/ /pubmed/35530591 http://dx.doi.org/10.1039/c9ra04338a Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/
spellingShingle Chemistry
Shimoda, Keiji
Koganei, Kazuto
Takeuchi, Tomonari
Matsunaga, Toshiyuki
Murakami, Miwa
Sakaebe, Hikari
Kobayashi, Hironori
Matsubara, Eiichiro
Structural characterization of an amorphous VS(4) and its lithiation/delithiation behavior studied by solid-state NMR spectroscopy
title Structural characterization of an amorphous VS(4) and its lithiation/delithiation behavior studied by solid-state NMR spectroscopy
title_full Structural characterization of an amorphous VS(4) and its lithiation/delithiation behavior studied by solid-state NMR spectroscopy
title_fullStr Structural characterization of an amorphous VS(4) and its lithiation/delithiation behavior studied by solid-state NMR spectroscopy
title_full_unstemmed Structural characterization of an amorphous VS(4) and its lithiation/delithiation behavior studied by solid-state NMR spectroscopy
title_short Structural characterization of an amorphous VS(4) and its lithiation/delithiation behavior studied by solid-state NMR spectroscopy
title_sort structural characterization of an amorphous vs(4) and its lithiation/delithiation behavior studied by solid-state nmr spectroscopy
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9069526/
https://www.ncbi.nlm.nih.gov/pubmed/35530591
http://dx.doi.org/10.1039/c9ra04338a
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