Ηλεκτροχημική ενίσχυση και συμπαραγωγή ηλεκτρικής ενέργειας και χρήσιμων χημικών προϊόντων σε κυψελίδες στερεού ηλεκτρολύτη

Abstract

The current study consists of two parts. In the first part, the effect of electrochemical promotion (EP) or non-faradaic electrochemical modification of catalytic activity (NEMCA) was studied, in the catalytic reaction of the total oxidation of propane on Pt and Rh films deposited on Y2O3-stabilized-ZrO2 (or YSZ), an O2- conductor, in the temperature range 420–520 oC. In the case of Pt/YSZ and for oxygen to propane ratios lower than the stoichiometric ratio it was found that the rate of propane oxidation could be reversibly enhanced by application of both positive and negative overpotentials (‘‘inverted volcano’’ behavior), by up to a factor of 1350 and 1130, respectively. The induced rate increase Δr exceeded the corresponding electrochemically controlled rate I/2F of O2- transfer through the solid electrolyte, resulting in absolute values of the apparent faradaic efficiency Λ=Δ r/(I/2F) up to 2330. The Rh/YSZ system exhibited similar EP behavior. Abrupt changes in the oxidation state of the rhodium catalyst, accompanied by changes in the catalytic rate, were observed by changing the O2 to propane ratio and catalyst potential. The highest rate increases, by up to a factor of 6, were observed for positive overpotentials with corresponding absolute values of faradaic efficiency K up to 830. Rate increases by up to a factor of 1.7 were observed for negative overpotentials. The observed EP behavior is explained by taking into account the mechanism of the reaction and the effect of catalyst potential on the binding strength of chemisorbed reactants and intermediates and on the oxidative state of the catalyst surface. The effect of electrochemical promotion (EP) of propane combustion was also studied over a platinum film catalyst deposited on sodium β-Al2O3, a Na+ conductor, in the temperature range 320–440oC. It was found that electrochemical pumping of sodium to the platinum surface markedly modifies its catalytic properties. For stoichiometric oxygen to propane ratio the system exhibited electrophobic behavior, i.e. addition of sodium resulted in decrease of the CO2 production rate. Relative changes in the catalytic rate by up to 60 times larger than the corresponding change in sodium coverage were measured. The observed behavior is explained by taking into account the reaction mechanism and the effect of the electrochemically controlled sodium coverage on the bonding of coadsorbed reactant species. Linear sweep and cyclic voltammetry were used to investigate the electrochemical processes taking place at the Pt/sodium β-Al2O3 interface under conditions of electrochemical promotion of propane combustion and in mixtures of O2, CO2 or propane with helium, at temperatures between 320 and 480oC. The number, position and magnitude of the peaks in the obtained voltammograms were found to depend on gas phase composition, temperature, starting potential and pre-scan conditions. The results showed that under conditions of electrochemical promotion of propane combustion more than one sodium phases can be formed on the Pt catalyst surface as a result of electrochemical pumping of sodium ions to it. The possible electrochemical reactions involving sodium species and the identity of the formed sodium phases during electrochemical pumping are discussed on the basis of the results obtained and those of former studies. In the second part of the study, the electrochemical performance of L58SCF (La0.58Sr0.4Co0.2Fe0.8O3-δ), LS2F (La0.9Sr1.1FeO4-δ), L78SCF (La0.78Sr0.2Co0.2Fe0.8O3-δ) and composite LSM (La0.65Sr0.3MnO3)/LSM-YSZ (50%wt-50%wt) cathode electrodes interfaced to a double layer CGO (Ce0.8Gd0.2O2)/YSZ electrolyte was studied using impedance spectroscopy and current-overpotential measurements. The experiments were carried out in the temperature range 600-850oC and, mainly, under flow of 21% O2/He mixture over the perovskite electrodes. The highest electrocatalytic activity for oxygen reduction was observed for the L78SCF cathode, according to the order: LS2F/CGO/YSZ £LSM/LSMSZ/CGO/YSZ<L58SCF/CGO/YSZ<L78SCF/CGO<YSZ. The composite electrode L58SCF-CGO was used in the last part of this study, combined with a carbon tolerant Au-modified (1% atomic ratio with respect to Ni) Ni-YSZ anode, prepared by combustion synthesis, to study the steam reforming of propane under stoichiometric oxygen to steam ratio. The experiments were carried out in the temperature range 600-750 oC, which is the target range for the successful commercialization of the intermediate temperature fuel cells. The main products of the reforming reaction were H2, CO, CO2 and CH4 with H2, CO to be strongly favored by the temperature increase. The maximum power density was found to be 34.3 mW/cm2 at 750oC with corresponding current density equal to i = 100 mA cm-2. The relatively low values of the current and power densities were mainly due to the large thickness of the electrolyte (0.5 mm). Overall, the system exhibited excellent stability during the experiment, which was confirmed through a 100 h stability test.