Conversion of Li2FeSbO5 to the Fe(III)/Fe(V) phase LiFeSbO5 via topochemical lithium extraction.

MARTÍNEZ DE IRUJO-LABALDE, Xabier, SCRIMSHIRE, Alex, BINGHAM, Paul, SUARD, Emanuelle and HAYWARD, Michael (2022). Conversion of Li2FeSbO5 to the Fe(III)/Fe(V) phase LiFeSbO5 via topochemical lithium extraction. Chemistry of Materials, 34 (5), 2468-2475.

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Reaction between Na2FeSbO5 and LiNO3 at 300 °C yields the metastable phase Li2FeSbO5 which is isostructural with the sodium “parent” phase (space group Pbna, a = 15.138(1) Å, b = 5.1440(3) Å, c = 10.0936(6) Å) consisting of an alternating stack of Li2Fe2O5 and Li2Sb2O5 sheets containing tetrahedral coordinated Fe3+ and octahedrally coordinated Sb5+, respectively. Further reaction between Li2FeSbO5 with NO2BF4 in acetonitrile at room temperature yields LiFeSbO5, which adopts an orthorhombic structure (space group Pbn21, a = 14.2943(4) Å, b = 5.2771(1) Å, c = 9.5610(3) Å) in which the LiFeO5 layers have shifted on lithium extraction, resulting in an octahedral coordination for the iron cations. 57Fe Mössbauer data indicate that the nominal Fe4+ cations present in LiFeSbO5 have disproportionated into a 1:1 combination of Fe3+ and Fe5+ centers which are ordered within the LiFeSbO5 structural framework. It is widely observed that Fe4+ centers tend to be unstable in delithiated Li–Fe–X–O phases currently proposed as lithium-ion battery cathode materials, so the apparent stability of highly oxidized Fe5+ centers in LiFeSbO5 is notable, suggesting cathode materials based on oxidizing Fe3+ could be possible. However, in this instance, the structural change which occurs on delithiation of Li2FeSbO5 prevents electrochemical cycling of this material.

Item Type: Article
Uncontrolled Keywords: 03 Chemical Sciences; 09 Engineering; Materials
Identification Number:
Page Range: 2468-2475
SWORD Depositor: Symplectic Elements
Depositing User: Symplectic Elements
Date Deposited: 11 Mar 2022 16:24
Last Modified: 24 Feb 2023 01:18

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