Dissemin is shutting down on January 1st, 2025

Published in

arXiv, 2019

DOI: 10.48550/arxiv.1911.11183

American Physical Society, Physical review B, 20(100), 2019

DOI: 10.1103/physrevb.100.205104

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Identification of ferrimagnetic orbitals preventing spinel degradation by charge ordering in LixMn2O4

This paper was not found in any repository, but could be made available legally by the author.
This paper was not found in any repository, but could be made available legally by the author.

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Abstract

Spinel Li$_x$Mn$_2$O$_4$ is a key cathode material that is used extensively in commercial Li-ion batteries. A challenge with this material has been that the capacity of the battery fades with cycling, an effect that can be traced to the presence of an anti-ferromagnetic insulator phase in the fully lithiated LiMn$_2$O$_4$ (LMO) and the associated charge disproportionation that drives distortions of the MnO$_6$ octahedra. Here, by combining x-ray magnetic Compton scattering experiments with parallel first-principles computations, we show that the anti-ferromagnetic phase of LMO is surrounded by a robust ferrimagnetic metallic phase, which becomes stable when even a small amount of Li is removed from or added to the charge-ordered LMO. In this surprising ferrimagnetic state, charge-ordering and octahedral distortions are found to be strongly suppressed. We identify the nature of the ferrimagnetic orbitals involved through theoretical and experimental analyses of the magnetic Compton scattering spectra.