Prelithiated SiOₓ/Graphite-NMC811 Cells: Capacity loss, Impedance Rise and Hidden Degradation Pathways Revealed Using Three-Electrode Diagnostics

Electrodes containing SiOx/graphite(Gr) materials are attractive as anodes for high-energy lithium-ion batteries. However, their mechanical deformation, electrochemical response, and impedance evolution during long-term cycling are strongly coupled, complicating accurate diagnosis of performance fade mechanisms. In this work, the behavior of electrochemically prelithiated SiOx/Gr anodes paired with NMC811 cathodes is systematically investigated using techniques that include in-situ dilatometry, three-electrode electrochemistry, and multiscale post-cycling microscopy. The SiOx/Gr electrode exhibits a maximum expansion of 49% upon lithiation to 10 mV vs. Li + /Li, with 84% of the expansion and 91% of the capacity being reversible. In full cells, relatively stable cycling with only 12% capacity fade over 500 cycles is observed. Three-electrode experiments reveal cell-level impedance growth, which is dominated by the NMC811 cathode: the SiOx/Gr anode exhibits minimal net impedance rise and an initial impedance decrease at low potentials. Despite this apparent electrochemical stability, crosssectional SEM, PFIB tomography, and cryo-STEM reveal irreversible anode thickening caused by the accumulation of an inorganic-rich solid electrolyte interphase (SEI) permeating the anode bulk. Electrode potential-shift analysis further demonstrates that Li + ions released from lithium reservoirs in the prelithiated anode masks true lithium inventory loss during aging. These results demonstrate that low-expansion SiOx/Gr anodes can simultaneously exhibit favorable cycling and impedance metrics while undergoing substantial, hidden degradation, underscoring the importance of electrode-resolved diagnostics for evaluating prelithiated silicon-based anodes.