A composite paste electrode based on Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF)—initially synthesized by solgel method—and multiwall carbon nanotube (MWCNT) as a cathode in fuel cells is developed. The composite pastes are pr...A composite paste electrode based on Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF)—initially synthesized by solgel method—and multiwall carbon nanotube (MWCNT) as a cathode in fuel cells is developed. The composite pastes are prepared by the direct mixing of BSCF:MWCNT at 90:10, 80:20 and 70:30 (% w/W). These electrodes are then characterized by the x-ray diffraction (XRD), scanning electron microscopy (SEM), nitrogen adsorption-desorption isotherm, electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The XRD and SEM confirm the inclusion and the uniform dispersal of the MWCNT within BSCF, respectively. The nitrogen adsorption isotherm study shows that the porosity of the composite paste electrode has been improved by two-fold from the BSCF electrode. The EIS and CV demonstrate that the higher ratios of MWCNT in the composites are critical in improving the electronic conductivity as well as the kinetics. It is also noticeable that the electrode has increased the catalysis of oxygen in 0.1 M KOH (pH 12.0). Cyclic voltammetric studies on the oxygen reduction reaction (ORR) suggest that the incorporation of MWCNT is vital in improving the electrode (cathode) properties of a fuel cell.展开更多
The nano ceramic Ba0.5Sr0.5Co0.2Fe0.8O3 (BSCF) powders have been synthesized by Sol-Gel process using nitrate based chemicals for SOFC applications since these powders are considered to be more promising cathode mater...The nano ceramic Ba0.5Sr0.5Co0.2Fe0.8O3 (BSCF) powders have been synthesized by Sol-Gel process using nitrate based chemicals for SOFC applications since these powders are considered to be more promising cathode materials for SOFC. Glycine was used as a chelant agent and ethylene glycol as a dispersant. The powders were calcined at 850℃/3 hr in the air using Thermolyne 47,900 furnace. These powders were characterized by employing SEM/EDS, XRD and TGA/DTA techniques. The SEM images BSCF powder indicate the presence of highly porous spherical particles with nano sizes. The XRD results shows the formation of BSCF perovskite phase at the calcination temperature of 850℃. From XRD line broadening technique, the average crystllite size of the BSCF powders were found to be around 9.15 - 11.83 nm and 13.63 - 17.47 nm for as prepared and after calcination at 850℃ respectively. The TGA plot shows that there is no weight loss after the temperature around 450℃ indicating completion of combustion.展开更多
The development of bi-functional electrocatalyst with high catalytic activity and stable performance for both oxygen evolution/reduction reactions(OER/ORR)in aqueous alkaline solution is key to realize practical appli...The development of bi-functional electrocatalyst with high catalytic activity and stable performance for both oxygen evolution/reduction reactions(OER/ORR)in aqueous alkaline solution is key to realize practical application of zinc-air batteries(ZABs).In this study,we reported a new porous nano-micro-composite as a bifunctional electrocatalyst for ZABs,devised by the in situ growth of metal-organic framework(MOF)nanocrystals onto the micrometersized Ba0.5Sr0.5Co0.8Fe0.2O3(BSCF)perovskite oxide.Upon carbonization,MOF was converted to porous nitrogen-doped carbon nanocages and ultrafine cobalt oxides and CoN4 nanoparticles dispersing inside the carbon nanocages,which further anchored on the surface of BSCF oxide.We homogeneously dispersed BSCF perovskite particles in the surfactant;subsequently,ZIF-67 nanocrystals were grown onto the BSCF particles.In this way,leaching of metallic or organic species in MOFs and the aggregation of BSCF were effectively suppressed,thus maximizing the number of active sites for improving OER.The BSCF in turn acted as catalyst to promote the graphitization of carbon during pyrolysis,as well as to optimize the transition metal-tocarbon ratio,thus enhancing the ORR catalytic activity.A ZAB fabricated from such air electrode showed outstanding performance with a potential gap of only 0.83 V at 5 mA cm-2 for OER/ORR.Notably,no obvious performance degradation was observed for the continuous charge-discharge operation for 1800 cycles over an extended period of 300 h.展开更多
A novel pulse 18O-16O isotopic exchange (PIE) technique for measurement of the rate of oxygen surface exchange of oxide ion conductors was presented. The technique employs a continuous flow packed-bed micro-reactor lo...A novel pulse 18O-16O isotopic exchange (PIE) technique for measurement of the rate of oxygen surface exchange of oxide ion conductors was presented. The technique employs a continuous flow packed-bed micro-reactor loaded with the oxide powder. The isothermal response to an 18O-enriched pulse passing through the reactor, thereby maintaining chemical equilibrium, is measured by on-line mass spectrometry. Evaluation of the apparent exchange rate follows from the uptake of 18O by the oxide at given reactor residence time and surface area available for exchange. The developed PIE technique is rapid, simple and highly suitable for screening and systematic studies. No rapid heating/quenching steps are required to facilitate 18O tracer anneal or analysis, as in other commonly used techniques based upon oxygen isotopic exchange. Moreover, the relative distribution of the oxygen isotopologues 18O2, 16O18O, and 16O2 in the effluent pulse provides insight into the mechanism of the oxygen exchange reaction. The PIE technique has been demonstrated by measuring the exchange rate of selected oxides with enhanced oxide ionic conductivity in the range of 350?900 oC. Analysis of the experimental data in terms of a model with two consecutive, lumped steps for the isotopic exchange reaction shows that for mixed conductors Ba0.5Sr0.5Co0.8Fe0.2O3-δ(BSCF) and La2NiO4+δ the reaction is limited by the apparent rate of dissociative adsorption of O2 molecules at the oxide surface. For yttria-stabilized zirconia (YSZ), a change-over takes place, from rate-limitations by oxygen incorporation below ∽800 oC to rate-limitations by O2 dissociative adsorption above this temperature. Good agreement is obtained with exchange rates reported for these materials in literature.展开更多
文摘A composite paste electrode based on Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF)—initially synthesized by solgel method—and multiwall carbon nanotube (MWCNT) as a cathode in fuel cells is developed. The composite pastes are prepared by the direct mixing of BSCF:MWCNT at 90:10, 80:20 and 70:30 (% w/W). These electrodes are then characterized by the x-ray diffraction (XRD), scanning electron microscopy (SEM), nitrogen adsorption-desorption isotherm, electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The XRD and SEM confirm the inclusion and the uniform dispersal of the MWCNT within BSCF, respectively. The nitrogen adsorption isotherm study shows that the porosity of the composite paste electrode has been improved by two-fold from the BSCF electrode. The EIS and CV demonstrate that the higher ratios of MWCNT in the composites are critical in improving the electronic conductivity as well as the kinetics. It is also noticeable that the electrode has increased the catalysis of oxygen in 0.1 M KOH (pH 12.0). Cyclic voltammetric studies on the oxygen reduction reaction (ORR) suggest that the incorporation of MWCNT is vital in improving the electrode (cathode) properties of a fuel cell.
文摘The nano ceramic Ba0.5Sr0.5Co0.2Fe0.8O3 (BSCF) powders have been synthesized by Sol-Gel process using nitrate based chemicals for SOFC applications since these powders are considered to be more promising cathode materials for SOFC. Glycine was used as a chelant agent and ethylene glycol as a dispersant. The powders were calcined at 850℃/3 hr in the air using Thermolyne 47,900 furnace. These powders were characterized by employing SEM/EDS, XRD and TGA/DTA techniques. The SEM images BSCF powder indicate the presence of highly porous spherical particles with nano sizes. The XRD results shows the formation of BSCF perovskite phase at the calcination temperature of 850℃. From XRD line broadening technique, the average crystllite size of the BSCF powders were found to be around 9.15 - 11.83 nm and 13.63 - 17.47 nm for as prepared and after calcination at 850℃ respectively. The TGA plot shows that there is no weight loss after the temperature around 450℃ indicating completion of combustion.
基金the support provided by the“Australian Government Research Training Program(RTP)Scholarship”at Curtin University,Perth,Australia。
文摘The development of bi-functional electrocatalyst with high catalytic activity and stable performance for both oxygen evolution/reduction reactions(OER/ORR)in aqueous alkaline solution is key to realize practical application of zinc-air batteries(ZABs).In this study,we reported a new porous nano-micro-composite as a bifunctional electrocatalyst for ZABs,devised by the in situ growth of metal-organic framework(MOF)nanocrystals onto the micrometersized Ba0.5Sr0.5Co0.8Fe0.2O3(BSCF)perovskite oxide.Upon carbonization,MOF was converted to porous nitrogen-doped carbon nanocages and ultrafine cobalt oxides and CoN4 nanoparticles dispersing inside the carbon nanocages,which further anchored on the surface of BSCF oxide.We homogeneously dispersed BSCF perovskite particles in the surfactant;subsequently,ZIF-67 nanocrystals were grown onto the BSCF particles.In this way,leaching of metallic or organic species in MOFs and the aggregation of BSCF were effectively suppressed,thus maximizing the number of active sites for improving OER.The BSCF in turn acted as catalyst to promote the graphitization of carbon during pyrolysis,as well as to optimize the transition metal-tocarbon ratio,thus enhancing the ORR catalytic activity.A ZAB fabricated from such air electrode showed outstanding performance with a potential gap of only 0.83 V at 5 mA cm-2 for OER/ORR.Notably,no obvious performance degradation was observed for the continuous charge-discharge operation for 1800 cycles over an extended period of 300 h.
文摘A novel pulse 18O-16O isotopic exchange (PIE) technique for measurement of the rate of oxygen surface exchange of oxide ion conductors was presented. The technique employs a continuous flow packed-bed micro-reactor loaded with the oxide powder. The isothermal response to an 18O-enriched pulse passing through the reactor, thereby maintaining chemical equilibrium, is measured by on-line mass spectrometry. Evaluation of the apparent exchange rate follows from the uptake of 18O by the oxide at given reactor residence time and surface area available for exchange. The developed PIE technique is rapid, simple and highly suitable for screening and systematic studies. No rapid heating/quenching steps are required to facilitate 18O tracer anneal or analysis, as in other commonly used techniques based upon oxygen isotopic exchange. Moreover, the relative distribution of the oxygen isotopologues 18O2, 16O18O, and 16O2 in the effluent pulse provides insight into the mechanism of the oxygen exchange reaction. The PIE technique has been demonstrated by measuring the exchange rate of selected oxides with enhanced oxide ionic conductivity in the range of 350?900 oC. Analysis of the experimental data in terms of a model with two consecutive, lumped steps for the isotopic exchange reaction shows that for mixed conductors Ba0.5Sr0.5Co0.8Fe0.2O3-δ(BSCF) and La2NiO4+δ the reaction is limited by the apparent rate of dissociative adsorption of O2 molecules at the oxide surface. For yttria-stabilized zirconia (YSZ), a change-over takes place, from rate-limitations by oxygen incorporation below ∽800 oC to rate-limitations by O2 dissociative adsorption above this temperature. Good agreement is obtained with exchange rates reported for these materials in literature.
