XPS on Li-Battery-Related Compounds: Analysis of Inorganic SEI Phases and a Methodology for Charge Correction

TL;DR

This paper presents a new charge correction methodology for XPS analysis of lithium battery materials, improving phase identification accuracy and enabling insights into ionic conductivities under different bias conditions.

Contribution

The study introduces a straightforward charge correction approach using core level BE separations, enhancing reliability of phase identification in battery-related inorganic compounds.

Findings

Charge correction improves phase identification accuracy.

BE separations serve as reliable constraints for phase analysis.

Method applied to real battery data reveals ionic conductivity insights.

Abstract

Accurate identification of chemical phases associated with the electrode and solid electrolyte interphase (SEI) is critical for understanding and controlling interfacial degradation mechanisms in lithium containing battery systems. To study these critical battery materials and interfaces X ray photoelectron spectroscopy (XPS) is a widely used technique that provides quantitative chemical insights. However, due to the fact that a majority of chemical phases relevant to battery interfaces are poor electronic conductors, phase identification that relies primarily on absolute XPS core level binding-energies (BEs) can be problematic. Charging during XPS measurements leads to BE shifts that can be difficult to correct. These difficulties are often exacerbated by the coexistence of multiple Li containing phases in the SEI with overlapping XPS core levels. To facilitate accurate phase identification of battery relevant phases, we propose a straightforward approach for removing charging effects from XPS data sets. We apply this approach to XPS data sets acquired from six battery relevant inorganic phases including lithium metal (Li0), lithium oxide (Li2O), lithium peroxide (Li2O2), lithium hydroxide (LiOH), lithium carbonate (Li2CO3), and lithium nitride (Li3N). Specifically, we demonstrate that BE separations between core levels present in a particular phase (e.g. BE separation between the O 1s and Li 1s core levels in Li2O) provide an additional constraint that can significantly improve reliability of phase identification. Finally, as an exemplary case we apply the charge-correction methodology to XPS data acquired from a symmetric cell based on a Li2S P2S5 solid electrolyte. This analysis demonstrates that accurately accounting for XPS BE shifts as a function of current-bias conditions can provide a direct probe of ionic conductivities associated with battery materials.