Abstract : The charge/discharge capacity of natural graphite anode in lithium secondary batteries was examined as a function of charge/discharge rate. When the natural graphite anode was galvanostatically cycled in the range of 0.0- 2.0 V (vs. Li/Li+), the charging capacity decreased with an increase in the charging rate, which is caused by an earlier approach to the charging cut-off (0.0 V) before the complete charging that is in turn caused by an ever-increasing overpotential at higher rates. Even if the overpotential of discharging reaction also increased at higher discharge rates, the discharging reaction took place in the range of 0.0-0.3 V that is far below the discharge cut-off (2.0 V). As a result, the discharge capacity was not affected by the discharge rate because all the lithium ions once intercalated are fully
discharged even at high current condition. As the overpotential of lithium deposition reaction also increased at high current condition, the charge capacity of natural graphite could be enlarged by lowering the charging cut-off voltage below 0.0 V. There is, however, a limitation for the lowering of cut-off voltage because the resistance for lithium deposition is smaller than that of lithium intercalation into graphite. When the charge cut-off voltage was lowered down to -0.04 V under 1C condition, lithium ions were inserted into graphite without lithium deposition such that the discharge capacity could be raised up to 11%.
Key words : Lithium secondary batteries, Natural graphite, Rate capability, Cut-off voltage