Asymmetric kinetics in the electrochemical chargedischarge reaction has been investigated in the two-phase coexistence system at LiFePO4 positive electrodes for rechargeable Li ion batteries. The analyses of the electrochemical polarization profiles obtained by galvanostatic-pulse cycles reveals that nucleation and mass-transport is rate determining process for anodic and cathodic (charge and discharge) reaction, respectively, at high-rate conditions. We suggest that present two-phase system of LiFePO4 FePO4 forms coreshell type construction in each particle or agglomerate of particles, where LiFePO4 prefer to reside at outer shell-region of particles maybe due to smaller interfacial energy with electrolytes.
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