Scalable Precursor-Assisted Synthesis of a High Voltage LiNiCoPO Cathode for Li-Ion Batteries.

A solid-solution cathode of LiCoPO-LiNiPO was investigated as a potential candidate for use with the LiTiO (LTO) anode in Li-ion batteries. A pre-synthesized nickel-cobalt hydroxide precursor is mixed with lithium and phosphate sources by wet ball milling, which results in the final product, LiNiCoPO (LNCP) by subsequent heat treatment. Crystal structure and morphology of the product were analyzed by X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). Its XRD patterns show that LNCP is primarily a single-phase compound and has olivine-type XRD patterns similar to its parent compounds, LiCoPO and LiNiPO. Synchrotron X-ray absorption spectroscopy (XAS) analysis, however, indicates that Ni doping in LiCoPO is unfavorable because Ni is not actively involved in the electrochemical reaction. Consequently, it reduces the charge storage capability of the LNCP cathode. Additionally, ex situ XRD analysis of cycled electrodes confirms the formation of the electrochemically inactive rock salt-type NiO phase. The discharge capacity of the LNCP cathode is entirely associated with the Co/Co redox couple. The electrochemical evaluation demonstrated that the LNCP cathode paired with the LTO anode produced a 3.12 V battery with an energy density of 184 Wh kg based on the cathode mass.