In Situ Electrochemical Detection of Silicon Anode Crystallization for Full-Cell Health Management

In this study, we investigate the relationship between the progressive lowering of the silicon (Si) anode potential during lithiation and the accompanying crystallization reaction to enable in situ electrochemical detection in Si-based full cells. Si–Li half cells were first analyzed by differential capacity (dQ/dV), revealing a crystallization feature near 0.05 V vs. Li+/Li, commonly associated with crystallization to Li15Si4. In the initial cycle, this signal was obscured by a dominant amorphization peak near 0.1 V; however, once amorphization was completed and the end-of-lithiation potential dropped below ~0.05 V in later cycles, a distinct crystallization peak became clearly resolvable. Under capacity-limited cycling that mimics full-cell operation, degradation-induced lowering of the Si-anode potential led to the appearance of the crystallization signal when the anode potential crossed this threshold. Based on these results, we extended the analysis to LiFePO4–Si three-electrode full cells and, by reparameterizing dQ/dV as a function of charge time, separated electrode-specific contributions and identified the Si crystallization feature within the full-cell response when N/P » 1. A simple degradation-modeling scenario further showed that in cells initially designed with N/P > 1, loss of anode active material can reduce the effective N/P, drive the Si potential into the crystallization window, and introduce a new peak in the full-cell dQ/dV curve associated with Si crystallization. These combined experimental and modeling results indicate that degradation-driven lowering of the Si-anode potential triggers crystallization and that this process can be detected in full cells via dQ/dV analysis. Practically, the emergence of the Si-crystallization feature provides an in situ marker that the effective N/P has drifted toward unity due to anode-dominated aging and may inform charge cut-off strategies to mitigate further Si-anode degradation.