Nb-doped SrFeO_(3−δ)(SFO)is used as a cathode in proton-conducting solid oxide fuel cells(H-SOFCs).First-principles calculations show that the SrFe0.9Nb0.1O_(3−δ)(SFNO)cathode has a lower energy barrier in the catho...Nb-doped SrFeO_(3−δ)(SFO)is used as a cathode in proton-conducting solid oxide fuel cells(H-SOFCs).First-principles calculations show that the SrFe0.9Nb0.1O_(3−δ)(SFNO)cathode has a lower energy barrier in the cathode reaction for H-SOFCs than the Nb-free SrFeO_(3−δ)cathode.Subsequent experimental studies show that Nb doping substantially enhances the performance of the SrFeO_(3−δ)cathode.Then,oxygen vacancies(VO)were introduced into SFNO using the microwave sintering method,further improving the performance of the SFNO cathode.The mechanism behind the performance improvement owing to VO was revealed using first-principles calculations,with further optimization of the SFNO cathode achieved by developing a suitable wet chemical synthesis route to prepare nanosized SFNO materials.This method significantly reduces the grain size of SFNO compared with the conventional solid-state reaction method,although the solid-state reaction method is generally used for preparing Nb-containing oxides.As a result of defect engineering and synthesis approaches,the SFNO cathode achieved an attractive fuel cell performance,attaining an output of 1764 mW·cm−2 at 700℃ and operating for more than 200 h.The manipulation of Nb-doped SrFeO_(3−δ)can be seen as a“one stone,two birds”strategy,enhancing cathode performance while retaining good stability,thus providing an interesting approach for constructing high-performance cathodes for H-SOFCs.展开更多
A La_(0.5)Ba_(0.5)MnO_(3-δ) oxide was prepared using the sol-gel technique.Instead of a pure phase,La_(0.5)Ba_(0.5)MnO_(3-δ) was discovered to be a combination of La_(0.7)Ba_(0.3)MnO_(3-δ) and BaMnO_(3).The in-situ...A La_(0.5)Ba_(0.5)MnO_(3-δ) oxide was prepared using the sol-gel technique.Instead of a pure phase,La_(0.5)Ba_(0.5)MnO_(3-δ) was discovered to be a combination of La_(0.7)Ba_(0.3)MnO_(3-δ) and BaMnO_(3).The in-situ production of La_(0.7)Ba_(0.3)MnO_(3-δ)+BaMnO_(3) nanocomposites enhanced the oxygen vacancy(Vo)formation compared to single-phase La_(0.7)Ba_(0.3)MnO_(3-δ) or BaMnO_(3),providing potential benefits as a cathode for fuel cells.Subsequently,La_(0.7)Ba_(0.3)MnO_(3-δ)+BaMnO_(3) nanocomposites were utilized as the cathode for proton-conducting solid oxide fuel cells(H-SOFCs),which significantly improved cell performance.At 700 C,H-SOFC with a La_(0.7)Ba_(0.3)MnO_(3-δ)+BaMnO_(3) nanocomposite cathode achieved the highest power density(1504 mW·cm^(-2))yet recorded for H-SOFCs with manganate cathodes.This performance was much greater than that of single-phase La_(0.7)Ba_(0.3)MnO_(3-δ)or BaMnO_(3) cathode cells.In addition,the cell demonstrated excellent working stability.First-principles calculations indicated that the La_(0.7)Ba_(0.3)MnO_(3-δ)/BaMnO_(3) interface was crucial for the enhanced cathode performance.The oxygen reduction reaction(ORR)free energy barrier was significantly lower at the La_(0.7)Ba_(0.3)MnO_(3-δ)/BaMnO_(3) interface than that at the La_(0.7)Ba_(0.3)MnO_(3-δ) or BaMnO_(3) surfaces,which explained the origin of high performance and gave a guide for the construction of novel cathodes for H-SOFCs.展开更多
Ceramic BaCe0.8Ho0.2O3-α with orthorhombic perovskite structure was prepared by conventional solid state reaction, and its conductivity and ionic transport number were measured by ac impedance spectroscopy and gas co...Ceramic BaCe0.8Ho0.2O3-α with orthorhombic perovskite structure was prepared by conventional solid state reaction, and its conductivity and ionic transport number were measured by ac impedance spectroscopy and gas concentration cell methods in the temperature range of 600-1000 ℃ in wet hydrogen and wet air, respectively. Using the ceramics as solid electrolyte and porous platinum as electrodes, the hydrogen-air fuel cell was constructed, and the cell performance at temperature from 600-1000 ℃ was examined. The results indicate that the specimen was a pure protonic conductor with the protonic transport number of 1 at temperature from 600-900 ℃ in wet hydrogen, a mixed conductor of proton and electron with the protonic transport number of 0.99 at 1000 ℃. The electronic conduction could be neglected in this case, thus the total conductivity in wet hydrogen was approximately regarded as protonic conductivity. In wet air, the specimen was a mixed conductor of proton, oxide ion and electron hole. The protonic transport numbers were 0.01-0.09, and the oxide-ionic transport numbers were 0.27-0.32. The oxide ionic conductivity was increased with the increase of temperature, but the protonic conductivity displayed a maximum at 900 ℃, due to the combined increase in mobility and depletion of the carriers. The fuel cell could work stably. At 1000 ℃, the maximum short-circuit current density and power output density were 346 mA/cm^2 and 80 mW/cm^2, respectively.展开更多
基金the National Natural Science Foundation of China(Nos.52302314 and 12274361).
文摘Nb-doped SrFeO_(3−δ)(SFO)is used as a cathode in proton-conducting solid oxide fuel cells(H-SOFCs).First-principles calculations show that the SrFe0.9Nb0.1O_(3−δ)(SFNO)cathode has a lower energy barrier in the cathode reaction for H-SOFCs than the Nb-free SrFeO_(3−δ)cathode.Subsequent experimental studies show that Nb doping substantially enhances the performance of the SrFeO_(3−δ)cathode.Then,oxygen vacancies(VO)were introduced into SFNO using the microwave sintering method,further improving the performance of the SFNO cathode.The mechanism behind the performance improvement owing to VO was revealed using first-principles calculations,with further optimization of the SFNO cathode achieved by developing a suitable wet chemical synthesis route to prepare nanosized SFNO materials.This method significantly reduces the grain size of SFNO compared with the conventional solid-state reaction method,although the solid-state reaction method is generally used for preparing Nb-containing oxides.As a result of defect engineering and synthesis approaches,the SFNO cathode achieved an attractive fuel cell performance,attaining an output of 1764 mW·cm−2 at 700℃ and operating for more than 200 h.The manipulation of Nb-doped SrFeO_(3−δ)can be seen as a“one stone,two birds”strategy,enhancing cathode performance while retaining good stability,thus providing an interesting approach for constructing high-performance cathodes for H-SOFCs.
基金supported by the National Natural Science Foundation of China(Grant Nos.52272216 and 51972183)the Hundred Youth Talents Program of Hunan,and the Startup Funding for Talents at University of South Chinathe support from the Hunan University Student Innovation and Entrepreneurship Training Program(Grant No.S202210555343)。
文摘A La_(0.5)Ba_(0.5)MnO_(3-δ) oxide was prepared using the sol-gel technique.Instead of a pure phase,La_(0.5)Ba_(0.5)MnO_(3-δ) was discovered to be a combination of La_(0.7)Ba_(0.3)MnO_(3-δ) and BaMnO_(3).The in-situ production of La_(0.7)Ba_(0.3)MnO_(3-δ)+BaMnO_(3) nanocomposites enhanced the oxygen vacancy(Vo)formation compared to single-phase La_(0.7)Ba_(0.3)MnO_(3-δ) or BaMnO_(3),providing potential benefits as a cathode for fuel cells.Subsequently,La_(0.7)Ba_(0.3)MnO_(3-δ)+BaMnO_(3) nanocomposites were utilized as the cathode for proton-conducting solid oxide fuel cells(H-SOFCs),which significantly improved cell performance.At 700 C,H-SOFC with a La_(0.7)Ba_(0.3)MnO_(3-δ)+BaMnO_(3) nanocomposite cathode achieved the highest power density(1504 mW·cm^(-2))yet recorded for H-SOFCs with manganate cathodes.This performance was much greater than that of single-phase La_(0.7)Ba_(0.3)MnO_(3-δ)or BaMnO_(3) cathode cells.In addition,the cell demonstrated excellent working stability.First-principles calculations indicated that the La_(0.7)Ba_(0.3)MnO_(3-δ)/BaMnO_(3) interface was crucial for the enhanced cathode performance.The oxygen reduction reaction(ORR)free energy barrier was significantly lower at the La_(0.7)Ba_(0.3)MnO_(3-δ)/BaMnO_(3) interface than that at the La_(0.7)Ba_(0.3)MnO_(3-δ) or BaMnO_(3) surfaces,which explained the origin of high performance and gave a guide for the construction of novel cathodes for H-SOFCs.
基金Project supported by the National Natural Science Foundation of China (No. 20171034) and the Natural Science Foundation of Education Department of Jiangsu Province (No. 04KID150218).
文摘Ceramic BaCe0.8Ho0.2O3-α with orthorhombic perovskite structure was prepared by conventional solid state reaction, and its conductivity and ionic transport number were measured by ac impedance spectroscopy and gas concentration cell methods in the temperature range of 600-1000 ℃ in wet hydrogen and wet air, respectively. Using the ceramics as solid electrolyte and porous platinum as electrodes, the hydrogen-air fuel cell was constructed, and the cell performance at temperature from 600-1000 ℃ was examined. The results indicate that the specimen was a pure protonic conductor with the protonic transport number of 1 at temperature from 600-900 ℃ in wet hydrogen, a mixed conductor of proton and electron with the protonic transport number of 0.99 at 1000 ℃. The electronic conduction could be neglected in this case, thus the total conductivity in wet hydrogen was approximately regarded as protonic conductivity. In wet air, the specimen was a mixed conductor of proton, oxide ion and electron hole. The protonic transport numbers were 0.01-0.09, and the oxide-ionic transport numbers were 0.27-0.32. The oxide ionic conductivity was increased with the increase of temperature, but the protonic conductivity displayed a maximum at 900 ℃, due to the combined increase in mobility and depletion of the carriers. The fuel cell could work stably. At 1000 ℃, the maximum short-circuit current density and power output density were 346 mA/cm^2 and 80 mW/cm^2, respectively.