Performance and degradation of a Li-ion battery reflect the transport and kinetics of related species within the battery's electrode microstructures. The variational multi-scale principle is adapted to a Li-ion battery system in order to improve the predictions of battery performance by including multi-scale and multiphysics phenomena among the particle aggregates in the electrode; this physics cannot be addressed by conventional homogenized approaches. The developed model is verified through the direct numerical solutions and compared with the conventional pseudo-2D (P2D) model method. The developed model has revealed more dynamic battery behaviors related to the variation of the microstructure—such as particle shape, tortuosity, and material composition—while the corresponding result from P2D shows a monotonous change within different structures.