Silicon‐Doped LiFePO₄ Single Crystals: Growth, Conductivity Behavior, and Diffusivity

Abstract Single crystals of silicon doped LiFePO₄ with a silicon content of 1% are grown successfully by the floating zone technique and characterized by single‐crystal and powder X‐ray diffraction, secondary ion mass spectroscopy, and chemical analysis. Electron paramagnetic resonance demonstrates the presence of only Fe²⁺; no traces of Fe³⁺ are found. Impedance spectroscopy as well as step‐function polarization/depolarization (DC) measurements are carried out using the cells Ti/LiFe(Si)PO₄/Ti and LiAl/LiI/LiFe(Si)PO₄/LiI/LiAl. The electronic and ionic conductivities as well as the Li‐diffusivity of the sample in the major crystallographic directions ([h00], [0k0], and [00l]) are determined. Within experimental error the transport properties along the b‐ and c‐axes are found to be the same but differ significantly from the a‐axis, which exhibits lower values. Compared to undoped LiFePO₄, Si‐doping leads to an increase of the ionic conductivity while the electronic conductivity decreases, which is in agreement with a donor effect. The activation energies of conductivities and diffusivities are interpreted in terms of defect chemistry and relevant Brouwer diagrams are given.