New Insights into the Behaviour of Commercial Silicon Electrode Materials via Empirical Fitting of Galvanostatic Charge‐Discharge Curves

Abstract Silicon (Si) materials for use in Lithium ion batteries (LIBs) are of continued interest to battery manufacturers. With an increasing number of commercially available Si materials, evaluating their performance becomes a challenge. Here, we use an empirical fitting function presented earlier to aid in the analysis of galvanostatic charge‐discharge data of commercial Si half‐cells with relatively high loading. We find that the fitting procedure is capable of detecting dynamic changes in the cell, such as reversible capacity fade of the Si electrode. This fading is found to be due to the highly lithiated Li2Si ↽⇀ Li3.5Si phase and that the behaviour is strongly dependent on the potential of this phase. EIS reveals that the Si electrode is responsible for the reversible behaviour due to progressive loss of Li+ leading to increasing resistance. SEM/EDX and XPS characterization are also employed to determine the origin of the irreversible resistance growth on the Si electrodes