Direct observation of the lithiation and de-lithiation in lithium batteries on the component and microstructural scale is still difficult. This work presents recent advances in MeV ion-beam analysis, enabling quantitative contact-free analysis of the spatially-resolved lithium content and state-of-charge (SoC) in all-solid-state lithium batteries via 3 MeV proton-based characteristic x-ray and gamma-ray emission analysis. The analysis is demonstrated on cross-sections of ceramic and polymer all-solid-state cells with LLZO and MEEP/LIBOB solid electrolytes. Different SoC are measured ex-situ and one polymer-based operando cell is charged at 333 K during analysis. The data unambiguously show the migration of lithium upon charging. Quantitative lithium concentrations are obtained by taking the physical and material aspects of the mixed cathodes into account. This quantitative lithium determination as a function of SoC gives insight into irreversible degradation phenomena of all-solid-state batteries during the first cycles and locations of immobile lithium. The determined SoC matches the electrochemical characterization within uncertainties. The presented analysis method thus opens up a completely new access to the state-of-charge of battery cells not depending on electrochemical measurements. Automated beam scanning and data-analysis algorithms enable a 2D quantitative Li and SoC mapping on the µm-scale, not accessible with other methods.
Raman imaging for LiCoO2 composite positive electrodes in all-solid-state lithium batteries using Li2S–P2S5 solid electrolytes