Spatial‐Dependent Coupling of Electrochemistry, Mass Transport, and Stress in Silicon‐Graphite Composite Electrodes for Lithium‐Ion Batteries

Abstract The commercialization of high‐capacity silicon materials in lithium‐ion batteries is hindered by significant volume changes. Composite anodes made from silicon and graphite, which increase battery capacity and maintain electrode structural stability, are receiving considerable attention. However, the spatial configuration of the active particles in the electrode is few investigated due to the complexity of experiments at the microscopic scale. Herein, this work focuses on electrochemical, mass transport, and stress coupling mechanisms by considering different spatial configurations of silicon and graphite. In situ electrochemical and stress measurements are first conducted to demonstrate the impact of the active material arrangement. Then, a 2D electrochemical‐mechanical model is developed considering the heterogeneity of electrochemical processes at the particle‐electrolyte interface. The results show that placing silicon in the upper active layer significantly reduces the ion transport resistance, while the graphite layer near the current collector provides a good conductive network for electron transport in the silicon layer, enhancing the performance of the composite electrode structure. By combining electrochemical and mechanical field models with experimental verification, this study deepens the understanding of composite electrode structure design, offering practical guidance for optimizing the spatial configuration of electrode materials to significantly improve battery performance.