Understanding the irreversible lithium loss in silicon anodes using multi-edge X-ray scattering analysis

Abstract

During the first charge-discharge cycle, silicon-based batteries show an important capacity loss because of the formation of the solid electrolyte interphase (SEI) and morphological changes due to expansion-contraction sequence upon alloying. To understand this first-cycle irreversibility, quantitative methods are needed to characterize the chemical environment of silicon and lithium in the bulk of the cycled electrodes. Here we report a methodology based on multi-edge X-ray Raman Scattering performed on model silicon electrodes prepared in fully lithiated and fully delithiated states after the first cycle. The spectra were recorded at the C, O, F and Li K edges, as well as Si L2,3 edge. They were analysed using linear combinations of both experimental and computed reference spectra. We used prototypical SEI compounds as Li2CO3, LiF and LiPF6, as well as electrode constituents as binder and conductive carbon, cristalline Si, native SiO2,LixSi phases (x being the lithiation index) to identify the main species, isolate their relative contributions, and quantitatively evaluate the proportions of organic and inorganic products. We find that 30% of the carbonates formed in the SEI during the lithiation are dissolved on delithiation, and that part of the Li15Si4 alloys remain present after delithiation. By combining electrochemical analysis and XRS results, we identify that 17% of the lithium lost in the first cycle is trapped in disconnected silicon particles, while 30% form a fluorine-rich stable SEI and 53% a carbonate-rich partially-dissolvable SEI. These results pave the way to systematic, reference data-informed, and modelling assisted studies of SEI characteristics in the bulk of electrodes prepared under controlled state-of-charge and state-of-health conditions.