Identifying different states of lithiation of Li4Ti5O12 spinel by energy-dispersive inelastic X-ray scattering (EDIXS) spectroscopy

Abstract

The Li₄Ti₅O₁₂ (LTO) compound has been investigated as an alternative negative electrode material for lithium ion batteries (LIBs), which are being used as energy storage devices in stationary systems as well as for electric vehicles due to their many interesting features. The LTO compound has shown remarkable Li-ion intercalation/de-intercalation reversibility, demonstrating also zero-strain volume change during the cycling process along with notable safety performance. Furthermore, LTO has a high voltage plateau in comparison with other negative material candidates, helping to avoid the deposition of metallic lithium in the dendrite form. Due to its performance and potential application in LIBs, a deep knowledge regarding the behavior of this LTO compound is of high interest. In this work, energy-dispersive resonant inelastic X-ray scattering (EDIXS) is used to fulfill this need. In addition, XANES measurements were carried out as complementary methodology. The results indicate that EDIXS can differentiate LTO chemical compounds (lithiated and de-lithiated) with high sensitivity, and is a reliable tool to perform chemical speciation analysis on such samples. In addition, the results confirm theoretical predictions regarding the composition of different oxidation states of titanium associated with different states of charge/lithiation of the LTO-spinel also. The proposed methodology can be easily applied to other lithium-based materials and beyond them, such as those based on sodium and novel technologies based on polyvalent cations including magnesium and aluminium.