Vacancy-driven anisotropic defect distribution in the battery-cathode material LiFePO4.

Li-ion mobility in LiFePO(4), a key property for energy applications, is impeded by Fe antisite defects (Fe(Li)) that form in select b-axis channels. Here we combine first-principles calculations, statistical mechanics, and scanning transmission electron microscopy to identify the origin of the effect: Li vacancies (V(Li)) are confined in one-dimensional b-axis channels, shuttling between neighboring Fe(Li). Segregation in select channels results in shorter Fe(Li)-Fe(Li) spans, whereby the energy is lowered by the V(Li)'s spending more time bound to end-point Fe(Li)'s. V(Li)-Fe(Li)-V(Li) complexes also form, accounting for observed electron energy loss spectroscopy features.