Electrochimica Acta, Vol.182, 342-350, 2015
Seebeck coefficients of cells with molten carbonates relevant for the metallurgical industry
We report Seebeck coefficients of electrochemical cells with molten carbonate mixtures as electrolytes and carbon dioxide vertical bar oxygen electrodes. The system is relevant for use of waste heat and off-gases with concentration of carbon dioxide different from air, as for example in the metallurgical industry. The coefficient is -1.25 mV K-1 for a nearly equimolar mixture of lithium and sodium carbonate with dispersed magnesium oxide at 750 degrees C, one bar total pressure and a pressure ratio of carbon dioxide to oxygen of 2:1. The value is slightly lower when sodium is replaced by potassium. The theoretical expression of the Seebeck coefficient was established using the theory of non-equilibrium thermodynamics. We used this expression to predict an increase to -1.4 mV K-1 when lowering the gas partial pressures to 0.015 and 0.2 bar, respectively, for carbon dioxide and oxygen, a gas composition that can represent that of the off-gases from a silicon furnace which we are concerned with. The absolute value of the Seebeck coefficient increases by 0.2 mV K-1 when the cell average temperature increases from 550 to 850 degrees C. The presence of a second component in the electrolyte increases the coefficient significantly above the values obtained with one component, compatible with a lowering of the transported entropy of the carbonate ion. A concentration cell, using the off-gas from the silicon furnace as anode gas and air as cathode gas, will add 0.14V at 550 degrees C to the absolute value of the potential. The series construction has the potential to offer a power density at matched load conditions in the order of 0.5 kW m(-2). (C) 2015 The Authors. Published by Elsevier Ltd.