Aluminium-doped LiFePO4 single crystals. Part II. Ionic conductivity, diffusivity and defect model.

We report on lithium ion conductivity and diffusivity along major crystallographic directions of Al-doped LiFePO4 single crystals. Impedance spectroscopy as well as galvanostatic polarization measurements have been carried out on the electronically blocking symmetric cell LiAl/LiI/LiFe(Al)PO4/LiI/LiAl. Neither ionic conductivity nor lithium diffusivity show anisotropy in the bc planes within the experimental error, but much lower values in the a-direction. Similar features were observed earlier by us for the pure single-crystal and the Si-doped single crystal. On Al-doping the ionic conductivity has increased while the electronic conductivity has decreased compared to undoped LiFePO4. Not only this donor doping effect but also the temperature dependence of ionic conductivity and of lithium-diffusivity are successfully interpreted in terms of lithium vacancies, holes and associates in the framework of a detailed defect chemical analysis. Ion-electron as well as ion-ion associates play a significant role in this system.