A recent transmission electron microscopy (TEM) method using precession electron diffraction (PED) was used to obtain LiFePO 4 and FePO 4 phase mapping at the nanometer-scale level on a large number of particles of sizes between 50 and 300 nm in a partially charged cathode. Despite the similarity of the two phases (the difference of lattice parameters is <5%), the method gives clear results that have been confirmed using high-resolution transmission electron microscopy (HRTEM) and energy-filtered transmission electron microscopy/electron energy loss spectroscopy (EFTEM/EELS) experiments. The PED maps show that the particles are either fully lithiated or fully delithiated and, therefore, bring a strong support to the domino-cascade model at the nanoscale level (scale of a particle). A coreÀshell model or spinodal decomposition at mesoscale (scale of agglomerates of particles) is possible. Size effects on the transformation are also discussed.

LiFePO4 and FePO4 phase distributions of entire cross-sectioned electrodes with various Li content are investigated from nanoscale to mesoscale, by transmission electron microscopy and by the new electron forward scattering diffraction technique. The distributions of the fully delithiated (FePO4) or lithiated particles (LiFePO4) are mapped on large fields of view (>100 × 100 μm(2)). Heterogeneities in thin and thick electrodes are highlighted at different scales. At the nanoscale, the statistical analysis of 64 000 particles unambiguously shows that the small particles delithiate first. At the mesoscale, the phase maps reveal a core-shell mechanism at the scale of the agglomerates with a preferential pathway along the electrode porosities. At larger scale, lithiation occurs in thick electrodes "stratum by stratum" from the surface in contact with electrolyte toward the current collector.