Extracting the Redox Orbitals in Li Battery Materials with High-Resolution X-Ray Compton Scattering Spectroscopy

Abstract

We present an incisive spectroscopic technique for directly probing redox orbitals based on bulk electron momentum density measurements via high-resolution x-ray Compton scattering. Application of our method to spinel LixMn2O4, a lithium ion battery cathode material, is discussed. The orbital involved in the lithium insertion and extraction process is shown to mainly be the oxygen 2p orbital. Moreover, the manganese 3d states are shown to experience spatial delocalization involving 0.16 electrons per Mn site during the battery operation. Our analysis provides a clear understanding of the fundamental redox process involved in the working of a lithium ion battery.

arXiv comment24 pages, 3 figures

References in corpus (11)

• Electronic structure and magnetism of Fe${}_{3-x}$V${}_x$X (X = Si, Ga and Al) alloys by the KKR-CPA method
• Compton scattering beyond the impulse approximation
• Influence of the Third Dimension of Quasi-Two-Dimensional Cuprate Superconductors on Angle-Resolved Photoemission Spectra
• Evolution of Mid-gap States and Residual 3-Dimensionality in La${}_{2-x}$Sr${}_x$CuO${}_4$
• Treatment of Correlation Effects in Electron Momentum Density: Density Fuctional Theory and Beyond
• Origin of electron-hole asymmetry in the scanning tunneling spectrum of $B{i}_{2}S{r}_{2}CaC{u}_2{O}_{8+\delta }$
• Observation of a strongly nested Fermi surface in the shape-memory alloy Ni[0.62]Al[0.38]
• A natural orbital method for the electron momentum distribution in matter
• Role of Oxygen Electrons in the Metal-Insulator Transition in the Magnetoresistive Oxide La${}_{2-2x}$Sr${}_{1+2x}$Mn${}_2$O${}_7$ Probed by Compton Scattering
• Bulk electronic structure of optimally doped Ba(Fe${}_{1-x}$Co${}_x$)${}_2$As${}_2$
• Anomalous electronic correlations in ground state momentum density of Al${}_{97}$Li${}_3$

Cited by in corpus (9)

• Spectroscopic Signature of Oxidized Oxygen States in Peroxides
• Non-destructive measurement of in-operando lithium concentration in batteries via x-ray Compton scattering
• Identifying a descriptor for d-orbital delocalization in cathodes of Li batteries based on x-ray Compton scattering
• Effect of Pore Formation on Redox-Driven Phase Transformation
• Identification of ferrimagnetic orbitals preventing spinel degradation by charge ordering in Li${}_x$Mn${}_2$O${}_4$
• High-resolution Compton spectroscopy using X-ray microcalorimeters
• Compton scattering study of strong orbital delocalization in a LiNiO${}_2$ cathode
• Redox oscillations in 18650-type lithium-ion cell revealed by in operando Compton scattering imaging
• Local electronic structure of dilute hydrogen in $\beta$-MnO${}_2$