Coupled Mechanical and Electrochemical Analyses of Three-Dimensional Reconstructed LiFePO₄ by Focused Ion Beam/Scanning Electron Microscopy in Lithium-Ion Batteries

Limited lifetime and performance degradation in lithium ion batteries in electrical vehicles and power tools is still a challenging obstacle which results from various interrelated processes, especially under specific conditions such as higher discharging rates (C-rates) and longer cycles. To elucidate these problems, it is very important to analyze electrochemical degradation from a mechanical stress point of view. Specifically, the goal of this study is to investigate diffusion-induced stresses and electrochemical degradation in three-dimensional (3D) reconstructed LiFePO₄. We generate a reconstructed microstructure by using a stack of focused ion beam-scanning electron microscopy (FIB/SEM) images combined with an electrolyte domain. Our previous two-dimensional (2D) finite element model is further improved to a 3D multiphysics one, which incorporates both electrochemical and mechanical analyses. From our electrochemistry model, we observe 95.6% and 88.3% capacity fade at 1.2 C and 2 C, respectively. To investigate this electrochemical degradation, we present concentration distributions and von Mises stress distributions across the cathode with respect to the depth of discharge (DoD). Moreover, electrochemical degradation factors such as total polarization and over-potential are also investigated under different C-rates. Further, higher total polarization is observed at the end of discharging, as well as at the early stage of discharging. It is also confirmed that lithium intercalation at the electrode-electrolyte interface causes higher over-potential at specific DoDs. At the region near the separator, a higher concentration gradient and over-potential are observed. We note that higher over-potential occurs on the surface of electrode, and the resulting concentration gradient and mechanical stresses are observed in the same regions. Furthermore, mechanical stress variations under different C-rates are quantified during the discharging process. With these coupled mechanical and electrochemical analyses, the results of this study may be helpful for detecting particle crack initiation.