An electrochemical-thermal-coupled model is used to predict performance of a Li-ion cell as well as its individual electrodes at various operating temperatures. The model is validated against the experimental data for constant current and pulsing conditions characteristic of hybrid electric vehicle (HEV) applications. The prediction of individual electrode potential is also compared with 3-electrode cell experimental data with good agreement. The predictive ability of the individual electrode behavior is very useful to address important issues related to electrode degradation and subzero performance of automotive Li-ion batteries. Copyright (C) 2009 John Wiley & Sons, Ltd.