The thermoelectric transport properties of Zr0.43Hf0.57 NiSn half-Heusler compounds were investigated for samples sintered with different spark plasma sintering(SPS)periods:8,32 and 72 min.By means of scanning transmi...The thermoelectric transport properties of Zr0.43Hf0.57 NiSn half-Heusler compounds were investigated for samples sintered with different spark plasma sintering(SPS)periods:8,32 and 72 min.By means of scanning transmission electron microscopy with a highangular annular dark-field detector(STEM-HAADF),it was found that sintering time affected the defect concentration,namely the amount of Ni interstitial atoms,and created locally ordered inclusions of full-Heusler phase.The structural information,phase composition and electrical transport properties could be consistently explained by the assumption that Ni interstitials give rise to an impurity band situated about 100 meV below the bottom of the conduction band via a self-doping behavior.The impurity band was found to merge with the conduction band for the sample with intermediate SPS time.The effect was ascribed to the gradual dissolution of full-Heusler phase inclusions and production of interstitial Ni defects,which eventually vanished for the sample with the longest sintering time.It was demonstrated that the modification of the density of states near the edge of the conduction band and enhanced overall charge carrier concentration provided by defect engineering led to overall 26%increase in the thermoelectric figure of merit(ZT)with respect to the other samples.展开更多
In this study,perovskite-type La_(0.7)Ca_(0.3)Co_(0.3)Fe_(0.6)M_(0.1)O_(3-δ)(M=Cu,Zn)powders were synthesized using a scalable reverse co-precipitation method,presenting them as novel materials for oxygen transport m...In this study,perovskite-type La_(0.7)Ca_(0.3)Co_(0.3)Fe_(0.6)M_(0.1)O_(3-δ)(M=Cu,Zn)powders were synthesized using a scalable reverse co-precipitation method,presenting them as novel materials for oxygen transport membranes.The comprehensive study covered various aspects including oxygen permeability,crystal structure,conductivity,morphology,CO_(2) tolerance,and long-term regenerative durability with a focus on phase structure and composition.The membrane La_(0.7)Ca_(0.3)Co_(0.3)Fe_(0.6)M_(0.1)O_(3-δ)exhibited high oxygen permeation fluxes,reaching up to 0.88 and 0.64 mL·min^(−1)·cm^(−2) under air/He and air/CO_(2) gradients at 1173 K,respectively.After 1600 h of CO_(2) exposure,the perovskite structure remained intact,showcasing superior CO_(2) resistance.A combination of first principles simulations and experimental measurements was employed to deepen the understanding of Cu/Zn substitution effects on the structure,oxygen vacancy formation,and transport behavior of the membranes.These findings underscore the potential of this highly CO_(2)-tolerant membrane for applications in high-temperature oxygen separation.The enhanced insights into the oxygen transport mechanism contribute to the advancement of next-generation membrane materials.展开更多
基金financially supported by German Research Foundation Priority Programme 1386(No.WE 2803/2-2)the European Union under Marie Sklodowska-Curie Program(W.J.X.)。
文摘The thermoelectric transport properties of Zr0.43Hf0.57 NiSn half-Heusler compounds were investigated for samples sintered with different spark plasma sintering(SPS)periods:8,32 and 72 min.By means of scanning transmission electron microscopy with a highangular annular dark-field detector(STEM-HAADF),it was found that sintering time affected the defect concentration,namely the amount of Ni interstitial atoms,and created locally ordered inclusions of full-Heusler phase.The structural information,phase composition and electrical transport properties could be consistently explained by the assumption that Ni interstitials give rise to an impurity band situated about 100 meV below the bottom of the conduction band via a self-doping behavior.The impurity band was found to merge with the conduction band for the sample with intermediate SPS time.The effect was ascribed to the gradual dissolution of full-Heusler phase inclusions and production of interstitial Ni defects,which eventually vanished for the sample with the longest sintering time.It was demonstrated that the modification of the density of states near the edge of the conduction band and enhanced overall charge carrier concentration provided by defect engineering led to overall 26%increase in the thermoelectric figure of merit(ZT)with respect to the other samples.
文摘In this study,perovskite-type La_(0.7)Ca_(0.3)Co_(0.3)Fe_(0.6)M_(0.1)O_(3-δ)(M=Cu,Zn)powders were synthesized using a scalable reverse co-precipitation method,presenting them as novel materials for oxygen transport membranes.The comprehensive study covered various aspects including oxygen permeability,crystal structure,conductivity,morphology,CO_(2) tolerance,and long-term regenerative durability with a focus on phase structure and composition.The membrane La_(0.7)Ca_(0.3)Co_(0.3)Fe_(0.6)M_(0.1)O_(3-δ)exhibited high oxygen permeation fluxes,reaching up to 0.88 and 0.64 mL·min^(−1)·cm^(−2) under air/He and air/CO_(2) gradients at 1173 K,respectively.After 1600 h of CO_(2) exposure,the perovskite structure remained intact,showcasing superior CO_(2) resistance.A combination of first principles simulations and experimental measurements was employed to deepen the understanding of Cu/Zn substitution effects on the structure,oxygen vacancy formation,and transport behavior of the membranes.These findings underscore the potential of this highly CO_(2)-tolerant membrane for applications in high-temperature oxygen separation.The enhanced insights into the oxygen transport mechanism contribute to the advancement of next-generation membrane materials.
