First-principles studies of the effects of impurities on the ionic and electronic conduction in LiFePO4

Olivine-type LiFePO4 is widely considered as a candidate for Li-ion battery electrodes, yet its applicability in the pristine state is limited due to poor ionic and electronic conduction. Doping can be employed to enhance the material's electrical conductivity. However, this should be understood as incorporating electrically active impurities to manipulate the concentration of native point defects such as lithium vacancies and small hole polarons which are responsible for ionic and electronic conduction, respectively, and not as generating band-like carriers. Possible effects of monovalent (Na, K, Cu, and Ag), divalent (Mg and Zn), trivalent (Al), tetravalent (Zr, C, and Si), and pentavalent (V and Nb) impurities on the ionic and electronic conductivities of LiFePO4 are analyzed based on results from first-principles density-functional theory calculations. We identify impurities that are effective (or ineffective) at enhancing the concentration of lithium vacancies or small hole polarons. Based on our studies, we discuss specific strategies for enhancing the electrical conductivity in LiFePO4 and provide suggestions for further experimental studies.

► Doping is a way to manipulate the native defects responsible for conduction. ► Impurities can be effective or ineffective at enhancing certain native defects. ► Specific strategies for enhancing the electrical conductivity are discussed.