In order to characterize the reaction mechanism of lithium-ion cells during charge and discharge, two experimental methods, calorimetry and staircase voltage step coulometry (SVSC), are examined. As a result of calorimetry during charge and discharge, the influence of previous treatment applied to the cell is observed in the heat generation behavior. SVSC gives kinetic information of the rate-determining step in the cell reaction. It is found that there is a slow-rate reaction besides the main cell reaction during charge and discharge. It is suggested that the irreversibility of the slow-rate reaction causes the voltage hysteresis between charge and discharge. The cell reaction mechanism is discussed, mainly focusing the reaction at the hard carbon anode used in the test cell.