5-V plateau observed for Li-rich Li1 + xMn2 - XO4 stoichiometric spinels containing low-temperature-grown Li2MnO3 as an impurity phase

Masahiro Kasai, Hideyuki Dohi, Shin Nishimura

研究成果: ジャーナルへの寄稿記事

抄録

The redox reaction of tetravalent Mn4 + ions has attracted much interest since it is considered that this reaction is closely related to the generation of high capacity in layered cathodes with excess lithium. We considered that to investigate materials, which include tetravalent Mn4 + ions and have a different crystal structure from Li2MnO3, is valuable for understanding the reaction mechanism. The result will reveal whether Mn4 + ion in the Li2MnO3 structure is essential or only existence of Mn4 + ion is sufficient for appearance of the high capacity. In this work, we investigated Li-rich Li1 + xMn2 - xO4 (x = 0.20, 0.25, 0.30, 0.33) stoichiometric spinels. For a Li content of x = 0.33, a capacity of 50 mAh g- 1 was observed in 5-V region. It is possible that the Li-rich spinel includes a small amount of Li 2MnO 3 impurity, which exhibits the 5-V plateau. No significant changes in lattice constants are observed from x = 0.25 to 0.33, which indicates generation of Li 2MnO 3. We estimated the amount as 9.2 wt.% for x = 0.33 by standard addition analysis, and true Li concentration of the spinel component as 0.23. However, the observed 5-V capacity cannot be attributed to only the impurity phase of Li 2MnO 3, because the specific capacity must exceed 540 mAh g - 1 to explain it. It is considered that the observed 5-V capacity is caused by two components of the Li-rich spinel and the other phase like a composite material of Li 2MnO 3/Li-rich spinel. The 5-V capacity for the pure spinel component estimated by extrapolating the 5-V capacity vs. impurity-concentration plot is 7.9 mAh g - 1.

元の言語英語
ページ(範囲)77-86
ページ数10
ジャーナルSolid State Ionics
289
DOI
出版物ステータス出版済み - 6 1 2016

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plateaus
Impurities
impurities
spinel
Ions
Temperature
Redox reactions
Lattice constants
ions
Lithium
Cathodes
Crystal structure
spinell
Composite materials
lithium
plots
cathodes
crystal structure
composite materials

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Materials Science(all)
  • Condensed Matter Physics

これを引用

5-V plateau observed for Li-rich Li1 + xMn2 - XO4 stoichiometric spinels containing low-temperature-grown Li2MnO3 as an impurity phase. / Kasai, Masahiro; Dohi, Hideyuki; Nishimura, Shin.

:: Solid State Ionics, 巻 289, 01.06.2016, p. 77-86.

研究成果: ジャーナルへの寄稿記事

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title = "5-V plateau observed for Li-rich Li1 + xMn2 - XO4 stoichiometric spinels containing low-temperature-grown Li2MnO3 as an impurity phase",
abstract = "The redox reaction of tetravalent Mn4 + ions has attracted much interest since it is considered that this reaction is closely related to the generation of high capacity in layered cathodes with excess lithium. We considered that to investigate materials, which include tetravalent Mn4 + ions and have a different crystal structure from Li2MnO3, is valuable for understanding the reaction mechanism. The result will reveal whether Mn4 + ion in the Li2MnO3 structure is essential or only existence of Mn4 + ion is sufficient for appearance of the high capacity. In this work, we investigated Li-rich Li1 + xMn2 - xO4 (x = 0.20, 0.25, 0.30, 0.33) stoichiometric spinels. For a Li content of x = 0.33, a capacity of 50 mAh g- 1 was observed in 5-V region. It is possible that the Li-rich spinel includes a small amount of Li 2MnO 3 impurity, which exhibits the 5-V plateau. No significant changes in lattice constants are observed from x = 0.25 to 0.33, which indicates generation of Li 2MnO 3. We estimated the amount as 9.2 wt.{\%} for x = 0.33 by standard addition analysis, and true Li concentration of the spinel component as 0.23. However, the observed 5-V capacity cannot be attributed to only the impurity phase of Li 2MnO 3, because the specific capacity must exceed 540 mAh g - 1 to explain it. It is considered that the observed 5-V capacity is caused by two components of the Li-rich spinel and the other phase like a composite material of Li 2MnO 3/Li-rich spinel. The 5-V capacity for the pure spinel component estimated by extrapolating the 5-V capacity vs. impurity-concentration plot is 7.9 mAh g - 1.",
author = "Masahiro Kasai and Hideyuki Dohi and Shin Nishimura",
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T1 - 5-V plateau observed for Li-rich Li1 + xMn2 - XO4 stoichiometric spinels containing low-temperature-grown Li2MnO3 as an impurity phase

AU - Kasai, Masahiro

AU - Dohi, Hideyuki

AU - Nishimura, Shin

PY - 2016/6/1

Y1 - 2016/6/1

N2 - The redox reaction of tetravalent Mn4 + ions has attracted much interest since it is considered that this reaction is closely related to the generation of high capacity in layered cathodes with excess lithium. We considered that to investigate materials, which include tetravalent Mn4 + ions and have a different crystal structure from Li2MnO3, is valuable for understanding the reaction mechanism. The result will reveal whether Mn4 + ion in the Li2MnO3 structure is essential or only existence of Mn4 + ion is sufficient for appearance of the high capacity. In this work, we investigated Li-rich Li1 + xMn2 - xO4 (x = 0.20, 0.25, 0.30, 0.33) stoichiometric spinels. For a Li content of x = 0.33, a capacity of 50 mAh g- 1 was observed in 5-V region. It is possible that the Li-rich spinel includes a small amount of Li 2MnO 3 impurity, which exhibits the 5-V plateau. No significant changes in lattice constants are observed from x = 0.25 to 0.33, which indicates generation of Li 2MnO 3. We estimated the amount as 9.2 wt.% for x = 0.33 by standard addition analysis, and true Li concentration of the spinel component as 0.23. However, the observed 5-V capacity cannot be attributed to only the impurity phase of Li 2MnO 3, because the specific capacity must exceed 540 mAh g - 1 to explain it. It is considered that the observed 5-V capacity is caused by two components of the Li-rich spinel and the other phase like a composite material of Li 2MnO 3/Li-rich spinel. The 5-V capacity for the pure spinel component estimated by extrapolating the 5-V capacity vs. impurity-concentration plot is 7.9 mAh g - 1.

AB - The redox reaction of tetravalent Mn4 + ions has attracted much interest since it is considered that this reaction is closely related to the generation of high capacity in layered cathodes with excess lithium. We considered that to investigate materials, which include tetravalent Mn4 + ions and have a different crystal structure from Li2MnO3, is valuable for understanding the reaction mechanism. The result will reveal whether Mn4 + ion in the Li2MnO3 structure is essential or only existence of Mn4 + ion is sufficient for appearance of the high capacity. In this work, we investigated Li-rich Li1 + xMn2 - xO4 (x = 0.20, 0.25, 0.30, 0.33) stoichiometric spinels. For a Li content of x = 0.33, a capacity of 50 mAh g- 1 was observed in 5-V region. It is possible that the Li-rich spinel includes a small amount of Li 2MnO 3 impurity, which exhibits the 5-V plateau. No significant changes in lattice constants are observed from x = 0.25 to 0.33, which indicates generation of Li 2MnO 3. We estimated the amount as 9.2 wt.% for x = 0.33 by standard addition analysis, and true Li concentration of the spinel component as 0.23. However, the observed 5-V capacity cannot be attributed to only the impurity phase of Li 2MnO 3, because the specific capacity must exceed 540 mAh g - 1 to explain it. It is considered that the observed 5-V capacity is caused by two components of the Li-rich spinel and the other phase like a composite material of Li 2MnO 3/Li-rich spinel. The 5-V capacity for the pure spinel component estimated by extrapolating the 5-V capacity vs. impurity-concentration plot is 7.9 mAh g - 1.

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