Surface fluorination and electrochemical behavior of petroleum cokes graphitized at medium and high temperatures for secondary lithium battery

The surface structure and electrochemical performance have been investigated of petroleum cokes heat-treated at 2100 and 2600 degrees C (abbreviated to PC2100 and PC2600) and those fluorinated by elemental fluorine at 200 and 300 degrees C. XPS study indicated that surface fluorine was covalently bonded to carbon and surface fluorine contents were in the range of 4.9-17.8 at.%. Surface oxygen was reduced by fluorination. BET surface areas were nearly the same before and after fluorination. Fluorination enhanced D-band intensity in two Raman shifts observed at 15 80 cm(-1) (G-band) and 1360 cm(-1) (D-band), indicating the increase in the surface disordering. At a high current density of 150 mA/g, the capacity increase was observed for PC2100 fluorinated at 200 degrees C and for PC2600 fluorinated at 200 and 300 degrees C. The most interesting result was the increase in first coulombic efficiencies by surface fluorination. First columbic efficiencies for PC2600 fluorinated at 300 degrees C were increased by 12.1% at 60 mA/g and by 25.8% at 150 mA/g, respectively. The impedance measurements showed that the resistances of surface films on carbon electrodes were increased by fluorination, however, the charge transfer resistances were decreased by 12.3% for PC2100 fluorinated at 200 degrees C, and by 27.5 and 6.4% for PC2600 fluorinated at 200 and 300 degrees C, respectively. The reduction of the charge transfer resistances was consistent with increase in the charge capacities for PC2100 fluorinated at 200 degrees C and PC2600 fluorinated at 200 and 300 degrees C. (c) 2005 Elsevier B.V. All rights reserved.