The impact of lithium extraction on the structural stabilities, electronic structures, bonding characteristics, and electrochemical performances of LiFePO 4 compound was investigated by first-principles technique. The results demonstrated that the partition scheme of electrons not only affects the calculated atomic charges but also the magnetic properties. In FePO 4 and LiFePO 4 compounds, all Fe ions take high spin arrangements and have large magnetic moments (MMs), while the MMs of other ions are very small. The magnetisms of Li x FePO 4 compounds are mainly originated form Fe ions. It was found that the changes in d band electrons of the transition metals do play an important role in determining the voltage of a battery (versus Li/Li + ). Furthermore, the variations in d band electrons also provide us a method to control the density of states (DOS) and carrier concentration at the Fermi energy. Our calculations confirmed that the substitution of Fe by Co and Ni ions leads to a voltage increase by about 0.70V and 1.23V respectively. According to the bond populations, it can be identified that strong covalent bonds are formed between O and P ions. The P–O bonds are much stronger than Fe–O ones. The partial DOSs further revealed that the covalent bonds in Li x FePO 4 are derived from the orbital overlaps between O 2s,2p and P 3s,3p states, and the overlap between Fe 3d and O 2p states. Such covalent bonds are of particularly importance for the excellent thermodynamic stabilities of the two-ends structures of Li x FePO 4 .