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

Sun Ruoheng; Jakes Peter; Eurich Svitlana; van Holt Desiree; Yang Shuo; Homberger Melanie; Simon Ulrich; Kungl Hans; Eichel Ruediger-A.

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

机译：用于锂离子电池的尖晶石型Limn2O4-阴极材料中的二次相形成：通过电子顺笔共振光谱定量痕量的Li2mNO3

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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 O-4 materials can be assessed. Accordingly, it is possible to estimate the amount of lithium on 16d-sites in the Li-rich manganese spinels.

机译：尖晶石型锂锰氧化物被认为是用于锂离子电池的有希望的阴极材料。痕量的Li 2 MnO 3通常在常见的高温，固态合成中作为锂 - 锰尖晶石中的二次相，影响尖晶石相中的总Li-Mn化学计量，从而影响了电化学性能。然而，常规分析技术几乎不能用常规分析技术形成Li 2 MnO 3的形成。在这项工作中，我们用不同的Li / Mn摩尔比合成锂 - 锰尖晶石，并证明了电子顺磁共振（EPR）能够在合成产物中定量痕量的Li 2 Li 2 Li 2 Li 2 Li 2 Li 2 Wt。％。结果表明，Li2MNO3二次相的形成是通过合成中的过量锂青少体的青睐。基于EPR数据的定量评价，可以评估Li1 + X MN2-X O-4材料中尖晶石相中的精确测定Li-Mn化学计量。因此，可以估计富富锰尖晶石中16D位点上的锂的量。

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来源
《Applied Magnetic Resonance》 |2018年第4期|共13页
作者
Sun Ruoheng; Jakes Peter; Eurich Svitlana; van Holt Desiree; Yang Shuo; Homberger Melanie; Simon Ulrich; Kungl Hans; Eichel Ruediger-A.;
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Forschungszentrum Julich Inst Energie &

Klimaforsch Grundlagen Elektrocem D-52425 Julich Germany;

Forschungszentrum Julich Inst Energie &

Klimaforsch Grundlagen Elektrocem D-52425 Julich Germany;

Forschungszentrum Julich Inst Energie &

Klimaforsch Grundlagen Elektrocem D-52425 Julich Germany;

Forschungszentrum Julich Inst Energie &

Klimaforsch Grundlagen Elektrocem D-52425 Julich Germany;

Rhein Westfal TH Aachen Inst Anorgan Chem D-52074 Aachen Germany;

Rhein Westfal TH Aachen Inst Anorgan Chem D-52074 Aachen Germany;

Rhein Westfal TH Aachen Inst Anorgan Chem D-52074 Aachen Germany;

Forschungszentrum Julich Inst Energie &

Klimaforsch Grundlagen Elektrocem D-52425 Julich Germany;

Forschungszentrum Julich Inst Energie &

Klimaforsch Grundlagen Elektrocem D-52425 Julich Germany;

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机译：用于锂离子电池的尖晶石型Limn2O4-阴极材料中的二次相形成：通过电子顺笔共振光谱定量痕量的Li2mNO3
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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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