Switching redox-active sites by valence tautomerism in prussian blue analogues AxMny[Fe(CN)6]· n H 2O (A: K, Rb): Robust frameworks for reversible Li storage

M. Okubo; D. Asakura; Y. Mizuno; J. D. Kim; T. Mizokawa; T. Kudo; I. Honma

doi:10.1021/jz100708b

Switching redox-active sites by valence tautomerism in prussian blue analogues A_xMn_y[Fe(CN)₆]· n H ₂O (A: K, Rb): Robust frameworks for reversible Li storage

M. Okubo, D. Asakura, Y. Mizuno, J. D. Kim, T. Mizokawa, T. Kudo, I. Honma^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

155 Citations (Scopus)

Abstract

The discovery of a new electrode material that provides a reversible Li ion insertion/extraction reaction is of primary importance for Li ion batteries. In this report, electrochemical Li ion insertion/extraction in valence tautomeric Prussian blue analogues A_xMn_y[Fe(CN)₆] (A: K, Rb) was investigated. Ex situ X-ray diffraction experiments revealed that the K salt without the valence tautomerism exhibits the Li ion insertion/extraction with a redox process of an Fe ion, while the Rb salt with the valence tautomerism exhibits that with a redox process of a Mn ion. Regardless of the redox-active metal ions, highly reversible Li ion storage was achieved. The electronic structure changes during the Li ion insertion/extraction are confirmed by XPS experiments.

Original language	English
Pages (from-to)	2063-2071
Number of pages	9
Journal	Journal of Physical Chemistry Letters
Volume	1
Issue number	14
DOIs	https://doi.org/10.1021/jz100708b
Publication status	Published - 2010 Jul 15
Externally published	Yes

ASJC Scopus subject areas

Materials Science(all)
Physical and Theoretical Chemistry

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title = "Switching redox-active sites by valence tautomerism in prussian blue analogues AxMny[Fe(CN)6]· n H 2O (A: K, Rb): Robust frameworks for reversible Li storage",

abstract = "The discovery of a new electrode material that provides a reversible Li ion insertion/extraction reaction is of primary importance for Li ion batteries. In this report, electrochemical Li ion insertion/extraction in valence tautomeric Prussian blue analogues AxMny[Fe(CN)6] (A: K, Rb) was investigated. Ex situ X-ray diffraction experiments revealed that the K salt without the valence tautomerism exhibits the Li ion insertion/extraction with a redox process of an Fe ion, while the Rb salt with the valence tautomerism exhibits that with a redox process of a Mn ion. Regardless of the redox-active metal ions, highly reversible Li ion storage was achieved. The electronic structure changes during the Li ion insertion/extraction are confirmed by XPS experiments.",

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T1 - Switching redox-active sites by valence tautomerism in prussian blue analogues AxMny[Fe(CN)6]· n H 2O (A

T2 - K, Rb): Robust frameworks for reversible Li storage

AU - Okubo, M.

AU - Asakura, D.

AU - Mizuno, Y.

AU - Kim, J. D.

AU - Mizokawa, T.

AU - Kudo, T.

AU - Honma, I.

PY - 2010/7/15

Y1 - 2010/7/15

N2 - The discovery of a new electrode material that provides a reversible Li ion insertion/extraction reaction is of primary importance for Li ion batteries. In this report, electrochemical Li ion insertion/extraction in valence tautomeric Prussian blue analogues AxMny[Fe(CN)6] (A: K, Rb) was investigated. Ex situ X-ray diffraction experiments revealed that the K salt without the valence tautomerism exhibits the Li ion insertion/extraction with a redox process of an Fe ion, while the Rb salt with the valence tautomerism exhibits that with a redox process of a Mn ion. Regardless of the redox-active metal ions, highly reversible Li ion storage was achieved. The electronic structure changes during the Li ion insertion/extraction are confirmed by XPS experiments.

AB - The discovery of a new electrode material that provides a reversible Li ion insertion/extraction reaction is of primary importance for Li ion batteries. In this report, electrochemical Li ion insertion/extraction in valence tautomeric Prussian blue analogues AxMny[Fe(CN)6] (A: K, Rb) was investigated. Ex situ X-ray diffraction experiments revealed that the K salt without the valence tautomerism exhibits the Li ion insertion/extraction with a redox process of an Fe ion, while the Rb salt with the valence tautomerism exhibits that with a redox process of a Mn ion. Regardless of the redox-active metal ions, highly reversible Li ion storage was achieved. The electronic structure changes during the Li ion insertion/extraction are confirmed by XPS experiments.

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Switching redox-active sites by valence tautomerism in prussian blue analogues A_xMn_y[Fe(CN)₆]· n H ₂O (A: K, Rb): Robust frameworks for reversible Li storage

Abstract

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