Secondary-Phase Formation in Spinel-Type LiMn2O4-Cathode Materials for Lithium-Ion Batteries: Quantifying Trace Amounts of Li2MnO3 by Electron Paramagnetic Resonance Spectroscopy

Secondary-Phase Formation in Spinel-Type LiMn2O4-Cathode Materials for Lithium-Ion Batteries:... Spinel-type lithium manganese oxides are considered as promising cathode materials for lithium-ion batteries. Trace amounts of Li2MnO3 usually occur as a secondary phase in lithium-manganese spinels in the common high-temperature, solid-state synthesis, affecting the overall Li–Mn stoichiometry in the spinel phase and thereby the electrochemical performance. However, the formation of Li2MnO3 lower than 1 wt.% can hardly be quantified by the conventional analytical techniques. In this work, we synthesized lithium-manganese spinels with different Li/Mn molar ratios and demonstrate that electron paramagnetic resonance (EPR) enables quantifying trace amounts of Li2MnO3 below 10−2 wt.% in the synthesized products. The results reveal that the formation of Li2MnO3 secondary phase is favored by lithium excess in the synthesis. Based on the quantitative evaluation of the EPR data, precise determining Li–Mn stoichiometry in the spinel phase in Li1+x Mn2−x O4 materials can be assessed. Accordingly, it is possible to estimate the amount of lithium on 16d-sites in the Li-rich manganese spinels. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Applied Magnetic Resonance Springer Journals

Secondary-Phase Formation in Spinel-Type LiMn2O4-Cathode Materials for Lithium-Ion Batteries: Quantifying Trace Amounts of Li2MnO3 by Electron Paramagnetic Resonance Spectroscopy

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Publisher
Springer Vienna
Copyright
Copyright © 2018 by Springer-Verlag GmbH Austria, part of Springer Nature
Subject
Physics; Solid State Physics; Spectroscopy/Spectrometry; Atoms and Molecules in Strong Fields, Laser Matter Interaction; Physical Chemistry; Organic Chemistry
ISSN
0937-9347
eISSN
1613-7507
D.O.I.
10.1007/s00723-018-0983-4
Publisher site
See Article on Publisher Site

Abstract

Spinel-type lithium manganese oxides are considered as promising cathode materials for lithium-ion batteries. Trace amounts of Li2MnO3 usually occur as a secondary phase in lithium-manganese spinels in the common high-temperature, solid-state synthesis, affecting the overall Li–Mn stoichiometry in the spinel phase and thereby the electrochemical performance. However, the formation of Li2MnO3 lower than 1 wt.% can hardly be quantified by the conventional analytical techniques. In this work, we synthesized lithium-manganese spinels with different Li/Mn molar ratios and demonstrate that electron paramagnetic resonance (EPR) enables quantifying trace amounts of Li2MnO3 below 10−2 wt.% in the synthesized products. The results reveal that the formation of Li2MnO3 secondary phase is favored by lithium excess in the synthesis. Based on the quantitative evaluation of the EPR data, precise determining Li–Mn stoichiometry in the spinel phase in Li1+x Mn2−x O4 materials can be assessed. Accordingly, it is possible to estimate the amount of lithium on 16d-sites in the Li-rich manganese spinels.

Journal

Applied Magnetic ResonanceSpringer Journals

Published: Feb 13, 2018

References

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