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Surface modification of active cathode particles is commonly observed in battery research as either a surface phase evolving during the cycling process, or intentionally engineered to improve capacity retention, rate capability, and/or thermal stability of the cathode material. Here, a continuum-scale model is developed to simulate the galvanostatic charge/discharge of a cathode particle with core-shell heterostructure. The particle is assumed to be comprised of a core material encapsulated by a thin layer of a second phase that has a different open-circuit voltage. The effect of the potential difference between the surface and bulk phases ( Ω ) on the kinetics of lithium intercalation and the galvanostatic charge/discharge profiles is studied at different values of Ω , C-rates, and exchange current densities. The difference between the Li chemical potential in the surface and bulk phases of the cathode particle results in a concentration difference between these two phases. This leads to a charge/discharge asymmetry in the galvanostatic voltage profiles, causing a decrease in the accessible capacity of the particle. These effects are more significant at higher magnitudes of surface-bulk potential difference. The proposed model provides detailed insight into the kinetics and voltage behavior of the intercalation/de-intercalation processes in core-shell heterostructure cathode particles.