The unique polarization behavior of LiFePO4 electrodes was investigated using mathematical simulations with a many-particle model, which have a non-monotonic potential profile for each LiFePO4 particle, and analyzed by the active population concept. The present simulations reveal two known polarization behaviors, namely the memory effect and path dependence. Notably, a hitherto unknown polarization behavior, the so-called relaxation-induced polarization (RIP), was also identified. The memory effect requires, at a minimum, a sequential four-step operation. By comparison, RIP is triggered only by a one-step operation, namely a long rest. In effect, the polarization associated with the memory effect and RIP was caused by a reduction of the active particles in the two-phase region via relaxation during a rest. The path-dependence mechanism was attributed to kinetically inhomogeneous reactions for each particle. We further found that narrowing the particle size distribution was an effective means to reduce polarization viz. the memory effect and path dependence of LiFePO4 electrodes. However, RIP could not be suppressed by narrowing the particle size distribution. A comprehensive understanding of these polarization behaviors with our model provides a more accurate way to estimate the state of charge in Li-ion batteries with LiFePO4 electrodes. (C) The Author(s) 2018. Published by ECS.