Experimental investigations on the electrochemical and thermal behaviour of LiCoPO4-based cathode

► The two-step mechanism during charging/discharging LiCoPO4 cathodes is illustrated. ► Thermal stability of LiCoPO4 cathodes with various states of charge is reported. ► Partially charged LiCoPO4 thermally stable up to 480 °C. ► Fully charged LiCoPO4 decomposes between 150 and 200 °C under release of O2 and CO2. ► Electrolyte and crystallite size influence the decomposition temperature.