Issue 26, 2024

Non-stoichiometry and electrochemical properties of lithiated iron hydroxysulfides

Abstract

LiFeOHS is a material with Li2(OH)2 layers intercalated between Fe2S2 planes. Its hydrothermal synthesis in various concentrations of LiOH yields materials with a high non-stoichiometry of the Li/Fe ratio which can be explained by partial substitution of Li+ for Fe2+ in the Li2(OH)2 layers. Thermogravimetry, X-ray diffraction and Mössbauer studies indicate that the charge balance is obtained by substitution of hydroxyl ions OH by oxide ions O2−. This material has been tested as an electrode for lithium-ion batteries against lithium metal. Specific capacities above 200 mA h g−1 at C/10 are achieved, involving 1 lithium per chemical formula when cycled between 1 V and 3 V vs. lithium. The first irreversible discharge leads to the insertion of one lithium atom and the evolution of hydrogen gas while iron remains in its +2-oxidation state. An original Li2OFeS oxysulfide is formed. The following reversible oxidation/reduction cycles involve the Fe3+/Fe2+ redox couple between the two limiting compositions: Li2OFeIIS and LiOFeIIIS.

Graphical abstract: Non-stoichiometry and electrochemical properties of lithiated iron hydroxysulfides

Article information

Article type
Paper
Submitted
10 feb 2024
Accepted
28 maj 2024
First published
05 jun 2024

Dalton Trans., 2024,53, 10991-11000

Non-stoichiometry and electrochemical properties of lithiated iron hydroxysulfides

C. Mir, D. Giaume, M. Morcrette, M. T. Sougrati, G. Wallez, M. Courty, M. Chakir and P. Barboux, Dalton Trans., 2024, 53, 10991 DOI: 10.1039/D4DT00405A

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