Li- Site and Metal-Site Ion Doping in Phosphate-Olivine LiCoPO4 by First-Principles Calculation

We present a first-principles investigation of the crystal and electronic structure as well as the average insertion voltage of the Li-site (by Na and Cr) and metal-site (by isovalent Ni, Zn, Ca, Mg and Mn and aliovalent Cu, Al, In, Mo and Zr) doped LiCoPO₄. The results show that both the Li-site doping and metal-site doping may reduce the volume change of the material during Li extraction/reinsertion process. The metal doped at Li-site will block the path of Li ion diffusion. The doping by aliovalent transition metals will introduce defect levels in the energy band. It could influence the conductivity insertion voltage.