In situ Fe K-edge X-ray absorption spectroscopy study during cycling of Li2FeSiO4 and Li2.2Fe0.9SiO4 Li ion battery materials

A.W. Brownrigg; G. Mountjoy; A.V. Chadwick; M. Alfredsson; W. Bras; J. Billaud; A.R. Armstrong; P.G. Bruce; R. Dominko; E.M. Kelder

doi:10.1039/c4ta06305h

In situ Fe K-edge X-ray absorption spectroscopy study during cycling of Li₂FeSiO₄ and Li_2.2Fe_0.9SiO₄ Li ion battery materials

A.W. Brownrigg, G. Mountjoy, A.V. Chadwick, M. Alfredsson, W. Bras, J. Billaud, A.R. Armstrong, P.G. Bruce, R. Dominko, E.M. Kelder

School of Chemistry

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Abstract

In situ X-ray Absorption Spectroscopy (XAS) results are presented for Li₂FeSiO₄ and Li_2.2Fe_0.9SiO₄, promising cathode materials for lithium-ion batteries. The aims are to establish the valence and local structure of Fe during charge and discharge to understand if the Fe³⁺/Fe⁴⁺ redox pair can be reached in the current battery design. It is found that the valence state changes between Fe²⁺ and Fe³⁺, with no evidence of Fe⁴⁺ before the onset of electrolyte degradation. There is a reversible contraction and extension of the Fe–O bond lengths during cycling while the Fe–Si distance remains constant, which underlines the stability of the Li₂FeSiO₄ material. The same observations apply to Li_2.2Fe_0.9SiO₄cathode material indicating that changing the stoichiometry does not provide any additional structural stability

Original language	English
Pages (from-to)	7314-7322
Number of pages	9
Journal	Journal of Materials Chemistry A
Volume	3
Issue number	14
Early online date	25 Feb 2015
DOIs	https://doi.org/10.1039/c4ta06305h
Publication status	Published - 14 Apr 2015

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10.1039/c4ta06305h

179932255_C4TA06305H_Billaud
Copyright 2015 the Authors. This work is made available online in accordance with the publisher’s policies. This is the author created, accepted version manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at: https://dx.doi.org/10.1039/C4TA06305H
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Brownrigg, A. W., Mountjoy, G., Chadwick, A. V., Alfredsson, M., Bras, W., Billaud, J., Armstrong, A. R., Bruce, P. G., Dominko, R., & Kelder, E. M. (2015). In situ Fe K-edge X-ray absorption spectroscopy study during cycling of Li₂FeSiO₄ and Li_2.2Fe_0.9SiO₄ Li ion battery materials. Journal of Materials Chemistry A, 3(14), 7314-7322. https://doi.org/10.1039/c4ta06305h

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title = "In situ Fe K-edge X-ray absorption spectroscopy study during cycling of Li2FeSiO4 and Li2.2Fe0.9SiO4 Li ion battery materials",

abstract = "In situ X-ray Absorption Spectroscopy (XAS) results are presented for Li2FeSiO4 and Li2.2Fe0.9SiO4, promising cathode materials for lithium-ion batteries. The aims are to establish the valence and local structure of Fe during charge and discharge to understand if the Fe3+/Fe4+ redox pair can be reached in the current battery design. It is found that the valence state changes between Fe2+ and Fe3+, with no evidence of Fe4+ before the onset of electrolyte degradation. There is a reversible contraction and extension of the Fe–O bond lengths during cycling while the Fe–Si distance remains constant, which underlines the stability of the Li2FeSiO4 material. The same observations apply to Li2.2Fe0.9SiO4 cathode material indicating that changing the stoichiometry does not provide any additional structural stability",

author = "A.W. Brownrigg and G. Mountjoy and A.V. Chadwick and M. Alfredsson and W. Bras and J. Billaud and A.R. Armstrong and P.G. Bruce and R. Dominko and E.M. Kelder",

year = "2015",

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doi = "10.1039/c4ta06305h",

language = "English",

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TY - JOUR

T1 - In situ Fe K-edge X-ray absorption spectroscopy study during cycling of Li2FeSiO4 and Li2.2Fe0.9SiO4 Li ion battery materials

AU - Brownrigg, A.W.

AU - Mountjoy, G.

AU - Chadwick, A.V.

AU - Alfredsson, M.

AU - Bras, W.

AU - Billaud, J.

AU - Armstrong, A.R.

AU - Bruce, P.G.

AU - Dominko, R.

AU - Kelder, E.M.

PY - 2015/4/14

Y1 - 2015/4/14

N2 - In situ X-ray Absorption Spectroscopy (XAS) results are presented for Li2FeSiO4 and Li2.2Fe0.9SiO4, promising cathode materials for lithium-ion batteries. The aims are to establish the valence and local structure of Fe during charge and discharge to understand if the Fe3+/Fe4+ redox pair can be reached in the current battery design. It is found that the valence state changes between Fe2+ and Fe3+, with no evidence of Fe4+ before the onset of electrolyte degradation. There is a reversible contraction and extension of the Fe–O bond lengths during cycling while the Fe–Si distance remains constant, which underlines the stability of the Li2FeSiO4 material. The same observations apply to Li2.2Fe0.9SiO4 cathode material indicating that changing the stoichiometry does not provide any additional structural stability

AB - In situ X-ray Absorption Spectroscopy (XAS) results are presented for Li2FeSiO4 and Li2.2Fe0.9SiO4, promising cathode materials for lithium-ion batteries. The aims are to establish the valence and local structure of Fe during charge and discharge to understand if the Fe3+/Fe4+ redox pair can be reached in the current battery design. It is found that the valence state changes between Fe2+ and Fe3+, with no evidence of Fe4+ before the onset of electrolyte degradation. There is a reversible contraction and extension of the Fe–O bond lengths during cycling while the Fe–Si distance remains constant, which underlines the stability of the Li2FeSiO4 material. The same observations apply to Li2.2Fe0.9SiO4 cathode material indicating that changing the stoichiometry does not provide any additional structural stability

UR - http://www.rsc.org/suppdata/ta/c4/c4ta06305h/c4ta06305h1.pdf

U2 - 10.1039/c4ta06305h

DO - 10.1039/c4ta06305h

M3 - Article

AN - SCOPUS:84925609607

SN - 2050-7488

VL - 3

SP - 7314

EP - 7322

JO - Journal of Materials Chemistry A

JF - Journal of Materials Chemistry A

IS - 14

ER -

In situ Fe K-edge X-ray absorption spectroscopy study during cycling of Li₂FeSiO₄ and Li_2.2Fe_0.9SiO₄ Li ion battery materials

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