The present study investigates the catalytic properties of metallic species commonly present in brown
coal (Ca, Fe, and Mg), towards Boudouard (CO2) gasification, by individually doping pure carbon black
with these species, and examining their electrochemical performance in a direct carbon fuel cell
(DCFC). Thermogravimetric analysis was used to study the effect of added catalysts on carbon oxidation
at 850 C and compared to those of chars produced from a Victorian brown coal. The relative catalytic
activities of dopants were found to increase from Mg < Fe < Ca, in the presence of CO2. The carbon black
fuels doped with the catalytic species, when tested in a direct carbon fuel cell, were also found to influ-
ence the fuel cell performance under both N2 and N2/CO2 anode purge gases in line with relative catalytic
activities of dopants. Electrochemical impedance spectroscopy measurements, under open circuit condi-
tions, were used to assess the nature of performance variations in fuel cell environments. Availability of
gaseous CO via in-situ Boudouard gasification of the fuel is believed to be the primary differentiating fac-
tor for various carbon fuels in cell operation. Finally, it was established that the catalytic dopants added to
the carbon fuel had an effect on the equilibrium oxygen partial pressure in the C/CO/CO2 system and
hence the open circuit voltage.