High power lithium-ion cells are a very promising energy source for practical hybrid vehicles. It is found that the impedance of the 18650 high-power cells using LiNi0.8Co0.2O2 chemistry increases with time during the beginning period of storage. A symmetric cell approach is developed to distinguish the anode and cathode effects on the impedance rise. Cathode impedance, especially charge-transfer resistance, is identified as the main component of the cell impedance and is most responsible for the rise of the cell impedance during storage at room temperature. With analysis of impedance spectra from a variety of cells, the charge-transfer process is thought to take place at the interface between the electrolyte solution and the surface of surface layers on the electrode. We also propose that the surface layers might be mixed conductors of electrons and lithium ions, instead of pure lithium-ion conductors. The nature of the surface layers on the cathode is likely different from that of the surface layers on the anode.