文章采用柠檬酸络合法制备了La_(0.6)Sr_(0.4)Co_(0.2)Fe_(0.8)O_(3-δ)钙钛矿,采用低温N_2物理吸附、X-射线衍射(X-ray diffraction,XRD)、氢气程序升温还原(hydrogen temperature programmed reduction,H_2-TPR)、氧气程序升温脱附(ox...文章采用柠檬酸络合法制备了La_(0.6)Sr_(0.4)Co_(0.2)Fe_(0.8)O_(3-δ)钙钛矿,采用低温N_2物理吸附、X-射线衍射(X-ray diffraction,XRD)、氢气程序升温还原(hydrogen temperature programmed reduction,H_2-TPR)、氧气程序升温脱附(oxygen temperature programmed desorption,O_2-TPD)和X-射线光电子能谱(X-ray photoelectron spectroscopy,XPS)表征了其物理化学性质,并考察了甲烷催化燃烧活性。结果表明,当柠檬酸/金属离子摩尔比(citric acid to metal ions molar ratio,CMMR)为1.25时,所制得的催化剂催化活性最佳。XRD表征结果表明,CMMR为1.25或1.50时,形成的钙钛矿晶型更完整。H_2-TPR表征结果表明,CMMR为1.25时,催化剂中的Fe^(4+)和Co^(3+)的还原温度较低,还原性能好。XPS表征结果表明,CMMR为1.25时,催化剂表面上吸附氧晶格氧之比最大。O_2-TPD表征结果表明,随着CMMR增加,催化剂中可移动晶格氧量减小,脱附温度增加,非化学计量比显著减小。CMMR为1.25时,催化剂表面吸附氧较易活化,形成活性物种。展开更多
采用柠檬酸-硝酸盐自蔓延燃烧法分别合成了Pr_(0.6)Sr_(0.4)Co_(0.2)Fe_(0.8)O_(3-δ)(PSCF)和Gd_(0.2)Ce_(0.8)O_(2-δ)(GDC)粉体,高温固相法合成La_(0.9)Sr_(0.1)Ga_(0.8)Mg_(0.2)O_(3-δ)(LSGM)电解质粉体。以LSGM为电解质,PSCF同时...采用柠檬酸-硝酸盐自蔓延燃烧法分别合成了Pr_(0.6)Sr_(0.4)Co_(0.2)Fe_(0.8)O_(3-δ)(PSCF)和Gd_(0.2)Ce_(0.8)O_(2-δ)(GDC)粉体,高温固相法合成La_(0.9)Sr_(0.1)Ga_(0.8)Mg_(0.2)O_(3-δ)(LSGM)电解质粉体。以LSGM为电解质,PSCF同时作为阴极和阳极,GDC作为功能层材料,构建了对称固体氧化物燃料电池PSCF│GDC│LSGM│GDC│PSCF。利用X射线衍射法研究材料的成相以及相互间的化学稳定性,交流阻抗法记录界面极化行为,用扫描电子显微镜观察电池的断面微结构,用自组装的测试系统评价电池输出性能。结果表明,合成的PSCF粉体呈立方钙钛矿结构,具有良好的氧化–还原可逆性。使用GDC功能层明显改善了氢气环境下PSCF与LSGM材料间的化学相容性以及电池的输出性能,800℃时,电极│电解质界面极化电阻从6.892?·cm^2下降到0.314?·cm^2;以加湿H_2(含体积分数3%的水蒸气)为燃料气,空气为氧化气时,单电池输出功率密度由269 m W/cm2增大至463 m W/cm^2。研究结果显示,PSCF是对称固体氧化物燃料电池良好的候选电极材料,GDC功能层对改善电池长期稳定性能具有潜在的应用价值。展开更多
La（0.6）Sr（0.4）Co（0.2）Fe（0.8）O（3-δ）（LSCF） anodes were infiltrated by Gd（0.2）Ce（0.8）O（1.9）GDC） nanoparticles to improve the oxygen evolution reaction（OER） performance of solid oxide electrolysis ce...La（0.6）Sr（0.4）Co（0.2）Fe（0.8）O（3-δ）（LSCF） anodes were infiltrated by Gd（0.2）Ce（0.8）O（1.9）GDC） nanoparticles to improve the oxygen evolution reaction（OER） performance of solid oxide electrolysis cells（SOECs） in CO2 electroreduction. The effect of GDC loading was investigated, and 10 wt% GDC nanoparticle infiltration of the LSCF（10 GDC/LSCF） anode results in the highest OER performance. Electrochemical impedance spectra measurements indicate that the infiltration by GDC nanoparticles greatly decreases the polarization resistance of the SOECs with the 10 GDC/LSCF anodes. The following distribution of relaxation time analysis suggests that four individual electrode processes are involved in the OER and that all of them are accelerated on the 10 GDC/LSCF anode. Three phase boundaries, surface oxygen vacancies, and bulk oxygen mobility increased, based on scanning electron microscopy and temperature-programmed desorption of O2 characterizations, and contributed to the enhancement of the four electrode processes of the OER and electrochemical performance of SOECs.展开更多
Single-phase perovskite La0.6Sr0.4Co0.8Fe0.2O3-δ has been successfully prepared by using citrate-EDTA complexation method at relatively low calcination temperature. The structure and thermal decomposition process of ...Single-phase perovskite La0.6Sr0.4Co0.8Fe0.2O3-δ has been successfully prepared by using citrate-EDTA complexation method at relatively low calcination temperature. The structure and thermal decomposition process of the complex precursor have been investigated by means of differential scanning calorimetry-thermal gravimetric analysis （DSC/TGA）, X-ray diffraction （XRD）, and Fourier transform infrared spectroscopic （FT-IR） measurements. The precursor decomposed completely and started to form perovskite-type oxide above 420 ℃ according to the differential scanning calorimetry （DSC） and thermal gravimetric analysis （TGA） results. Single-phase perovskite La0.6Sr0.4Co0.8Fe0.2O3-δ obtained has been confirmed from the XRD pattern, and no peak of SrCO3 was found by XRD of the oxides synthesized at a relatively low temperature of 800℃. The reducibility of La0.6Sr0.4Co0.8Fe0.2O3-δ was also characterized by the temperature programmed reduction （TPR） technique. Disk shaped dense La0.6Sr0.4Co0.8Fe0.2O3-δ membrane was prepared by the isostatical pressing method. The oxygen flux rate of dense La0.6Sr0.4Co0.8Fe0.2O3-δ membrane was （2.8-18）× 10^-8 mol/（cm^2.s） in the temperature range of 800-1000 ℃.展开更多
The La0.6Ba0.4Co0.2Fe0.8O3 (LBCF) nano ceramic powders were prepared by Sol-Gel process using nitrate based chemicals for SOFC applications since these powders are considered to be more promising cathode materials for...The La0.6Ba0.4Co0.2Fe0.8O3 (LBCF) nano ceramic powders were prepared by Sol-Gel process using nitrate based chemicals for SOFC applications since these powders are considered to be more promising cathode materials for SOFC. Citric acid was used as a chelant agent and ethylene glycol as a dispersant. The powders were calcined at 650oC/6 h, 900oC/3 h in air using Thermolyne 47,900 furnace. These powders were charac terized by SEM/EDS, XRD and Porosimetry techniques. The SEM images indicate that the particle sizes of the LBCF powders are in the range of 50 - 200 nm. The LBCF perovskite phases are seen from the XRD patterns. From XRD Line broadening technique, the average particle size for the powders (as prepared and calcined at 650oC/6 h and 900oC/3 h) were found to be around 12.97 nm, 22.24 nm and 26 nm respectively. The surface area of the LBCF powders for the as prepared and calcined at 650oC were found to be 28.92 and 19.54 m2/g respectively.展开更多
Mixed ionic-electronic conductors in the family of LaxSr1-xCoyFe1-y O3-δ have been widely studied as cathode materials for solid oxide fuel cells （SOFCs）. However, the long-term stability was a concern. Here we rep...Mixed ionic-electronic conductors in the family of LaxSr1-xCoyFe1-y O3-δ have been widely studied as cathode materials for solid oxide fuel cells （SOFCs）. However, the long-term stability was a concern. Here we report our findings on the effect of a thin film coating of La0.85Sr0.15MnO3-δ （LSM） on the performance of a porous La0.6Sr0.4Co0.2Feo.8O3-δ（LSCF） cathode. When the thicknesses of the LSM coatings are appropriate, an LSM-coated LSCF electrode showed better stability and lower polarization （or higher activity） than the blank LSCF cathode without LSM infiltration. An anode-supported cell with an LSM-infiltrated LSCF cathode demonstrated at 825 ℃ a peak power density of -1.07 W/cm2, about 24% higher than that of the same cell without LSM infiltration （-0.86 W/cm2）. Further, the LSM coating enhanced the stability of the electrode; there was little degradation in performance for the cell with an LSM-infiltrated LSCF cathode during 100 h operation.展开更多
Effects of SO2 in ambient air on the performance and durability of solid oxide fuel cell（SOFC） cathode were evaluated by galvanostatic measurement. Comparison between two cathode materials was made to consider the c...Effects of SO2 in ambient air on the performance and durability of solid oxide fuel cell（SOFC） cathode were evaluated by galvanostatic measurement. Comparison between two cathode materials was made to consider the cathode degradation mechanisms. The degradation performance is associated with a slow decomposition of the La0.6Sr0.4Co0.2Fe0.8O3（LSCF） due to the segregation of strontium oxide. Negligible deterioration for （La0.7Sr0.3）MnO3 （LSM） cathode was caused by SO2 poisoning under a current density of 200 mA/cm2. Metal sulphate formation may explain a slight deterioration under increasing high the concentration of SO2. It was verified that the poisoning mechanism for the two cathode materials resulted from the gradual decomposition of the cathode materials.展开更多
Fluidized bed reactor is widely used in coal char-CO2 gasification. In this work, the production of syngas by using a fluidized bed gasification technique was first investigated and then the effect of the produced syn...Fluidized bed reactor is widely used in coal char-CO2 gasification. In this work, the production of syngas by using a fluidized bed gasification technique was first investigated and then the effect of the produced syngas on the performance of the solid oxide fuel cell with a configuration of La0.4Sr0.6Co0.2 Fe0.7 Nb0.1O3-δ//La0.8Sr0.2Ga0.83Mg0.17O3-δ//La0.4Sr0.6Co0.2Fe0.7Nb0.1O3-δ（LSCFN//LSGM//LSCFN） was studied. During the syngas production, we found that the volume fraction of CO increased with the increment of gasification temperature, and it reached a maximum value of 88.8%, corresponding to a composition of 0.76% H2, 88.8% CO, and 10.44% CO2, when the ratio of oxygen mass flow rate to that of coal char （Mo2/Mchar） increased to 0.29. In the following utilization of the produced syngas in solid oxide fuel cells, it was found that the increasing CO volume fraction in the syngas results in a gradual increase of the peak power density of the LSCFN//LSGM//LSCFN cell. The maximum peak power density of 410 mW/cm^2 was achieved for the syngas produced at 0.29 of Mo2/Mchar. In the stability test, the cell voltage decreased by 4% at a constant current density of 0.475 A/cm^2 after 54 h when fueled with the syngas with the composition of 0.76% H2, 88.8% CO, and 10.44% CO2. It reveals that a carbon deposition with the content of 13.66% in the anode is attributed to the cell performance degradation.展开更多
文摘文章采用柠檬酸络合法制备了La_(0.6)Sr_(0.4)Co_(0.2)Fe_(0.8)O_(3-δ)钙钛矿,采用低温N_2物理吸附、X-射线衍射(X-ray diffraction,XRD)、氢气程序升温还原(hydrogen temperature programmed reduction,H_2-TPR)、氧气程序升温脱附(oxygen temperature programmed desorption,O_2-TPD)和X-射线光电子能谱(X-ray photoelectron spectroscopy,XPS)表征了其物理化学性质,并考察了甲烷催化燃烧活性。结果表明,当柠檬酸/金属离子摩尔比(citric acid to metal ions molar ratio,CMMR)为1.25时,所制得的催化剂催化活性最佳。XRD表征结果表明,CMMR为1.25或1.50时,形成的钙钛矿晶型更完整。H_2-TPR表征结果表明,CMMR为1.25时,催化剂中的Fe^(4+)和Co^(3+)的还原温度较低,还原性能好。XPS表征结果表明,CMMR为1.25时,催化剂表面上吸附氧晶格氧之比最大。O_2-TPD表征结果表明,随着CMMR增加,催化剂中可移动晶格氧量减小,脱附温度增加,非化学计量比显著减小。CMMR为1.25时,催化剂表面吸附氧较易活化,形成活性物种。
文摘采用柠檬酸-硝酸盐自蔓延燃烧法分别合成了Pr_(0.6)Sr_(0.4)Co_(0.2)Fe_(0.8)O_(3-δ)(PSCF)和Gd_(0.2)Ce_(0.8)O_(2-δ)(GDC)粉体,高温固相法合成La_(0.9)Sr_(0.1)Ga_(0.8)Mg_(0.2)O_(3-δ)(LSGM)电解质粉体。以LSGM为电解质,PSCF同时作为阴极和阳极,GDC作为功能层材料,构建了对称固体氧化物燃料电池PSCF│GDC│LSGM│GDC│PSCF。利用X射线衍射法研究材料的成相以及相互间的化学稳定性,交流阻抗法记录界面极化行为,用扫描电子显微镜观察电池的断面微结构,用自组装的测试系统评价电池输出性能。结果表明,合成的PSCF粉体呈立方钙钛矿结构,具有良好的氧化–还原可逆性。使用GDC功能层明显改善了氢气环境下PSCF与LSGM材料间的化学相容性以及电池的输出性能,800℃时,电极│电解质界面极化电阻从6.892?·cm^2下降到0.314?·cm^2;以加湿H_2(含体积分数3%的水蒸气)为燃料气,空气为氧化气时,单电池输出功率密度由269 m W/cm2增大至463 m W/cm^2。研究结果显示,PSCF是对称固体氧化物燃料电池良好的候选电极材料,GDC功能层对改善电池长期稳定性能具有潜在的应用价值。
基金This work was supported by the National Key R&D Program of China(2017YFA0700102)the National Natural Science Foundation of China(21703237,21573222,91545202)+1 种基金Dalian Institute of Chemical Physics(DICP DMTO201702)the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB17020200)and CAS Youth Innovation Promotion(2015145)~~
文摘La（0.6）Sr（0.4）Co（0.2）Fe（0.8）O（3-δ）（LSCF） anodes were infiltrated by Gd（0.2）Ce（0.8）O（1.9）GDC） nanoparticles to improve the oxygen evolution reaction（OER） performance of solid oxide electrolysis cells（SOECs） in CO2 electroreduction. The effect of GDC loading was investigated, and 10 wt% GDC nanoparticle infiltration of the LSCF（10 GDC/LSCF） anode results in the highest OER performance. Electrochemical impedance spectra measurements indicate that the infiltration by GDC nanoparticles greatly decreases the polarization resistance of the SOECs with the 10 GDC/LSCF anodes. The following distribution of relaxation time analysis suggests that four individual electrode processes are involved in the OER and that all of them are accelerated on the 10 GDC/LSCF anode. Three phase boundaries, surface oxygen vacancies, and bulk oxygen mobility increased, based on scanning electron microscopy and temperature-programmed desorption of O2 characterizations, and contributed to the enhancement of the four electrode processes of the OER and electrochemical performance of SOECs.
基金Sponsored by SRF for ROCS, key lab of enhanced heat transfer and energy conservation (MOE)Guangdong provincial natural science foundation (04020126).
文摘Single-phase perovskite La0.6Sr0.4Co0.8Fe0.2O3-δ has been successfully prepared by using citrate-EDTA complexation method at relatively low calcination temperature. The structure and thermal decomposition process of the complex precursor have been investigated by means of differential scanning calorimetry-thermal gravimetric analysis （DSC/TGA）, X-ray diffraction （XRD）, and Fourier transform infrared spectroscopic （FT-IR） measurements. The precursor decomposed completely and started to form perovskite-type oxide above 420 ℃ according to the differential scanning calorimetry （DSC） and thermal gravimetric analysis （TGA） results. Single-phase perovskite La0.6Sr0.4Co0.8Fe0.2O3-δ obtained has been confirmed from the XRD pattern, and no peak of SrCO3 was found by XRD of the oxides synthesized at a relatively low temperature of 800℃. The reducibility of La0.6Sr0.4Co0.8Fe0.2O3-δ was also characterized by the temperature programmed reduction （TPR） technique. Disk shaped dense La0.6Sr0.4Co0.8Fe0.2O3-δ membrane was prepared by the isostatical pressing method. The oxygen flux rate of dense La0.6Sr0.4Co0.8Fe0.2O3-δ membrane was （2.8-18）× 10^-8 mol/（cm^2.s） in the temperature range of 800-1000 ℃.
文摘The La0.6Ba0.4Co0.2Fe0.8O3 (LBCF) nano ceramic powders were prepared by Sol-Gel process using nitrate based chemicals for SOFC applications since these powders are considered to be more promising cathode materials for SOFC. Citric acid was used as a chelant agent and ethylene glycol as a dispersant. The powders were calcined at 650oC/6 h, 900oC/3 h in air using Thermolyne 47,900 furnace. These powders were charac terized by SEM/EDS, XRD and Porosimetry techniques. The SEM images indicate that the particle sizes of the LBCF powders are in the range of 50 - 200 nm. The LBCF perovskite phases are seen from the XRD patterns. From XRD Line broadening technique, the average particle size for the powders (as prepared and calcined at 650oC/6 h and 900oC/3 h) were found to be around 12.97 nm, 22.24 nm and 26 nm respectively. The surface area of the LBCF powders for the as prepared and calcined at 650oC were found to be 28.92 and 19.54 m2/g respectively.
基金supported by the Department of Energy (National Energy Technology Laboratory) SECA Core Technology Program under Award Number DE-NT0006557 and DE-FE0009652by NSFC under grant No.51002182
文摘Mixed ionic-electronic conductors in the family of LaxSr1-xCoyFe1-y O3-δ have been widely studied as cathode materials for solid oxide fuel cells （SOFCs）. However, the long-term stability was a concern. Here we report our findings on the effect of a thin film coating of La0.85Sr0.15MnO3-δ （LSM） on the performance of a porous La0.6Sr0.4Co0.2Feo.8O3-δ（LSCF） cathode. When the thicknesses of the LSM coatings are appropriate, an LSM-coated LSCF electrode showed better stability and lower polarization （or higher activity） than the blank LSCF cathode without LSM infiltration. An anode-supported cell with an LSM-infiltrated LSCF cathode demonstrated at 825 ℃ a peak power density of -1.07 W/cm2, about 24% higher than that of the same cell without LSM infiltration （-0.86 W/cm2）. Further, the LSM coating enhanced the stability of the electrode; there was little degradation in performance for the cell with an LSM-infiltrated LSCF cathode during 100 h operation.
基金Supported by the National Natural Science Foundation of China(No.50872041)the Research Funds of Industrial Technology Research and Development Projects of Jilin Province, China(No.JF2012C024)+1 种基金the Natural Science Foundation of Jilin Province,China(No.201215109)the Science and Technology Research Projects of Education Department of Jilin Province, China(No.2011205)
文摘Effects of SO2 in ambient air on the performance and durability of solid oxide fuel cell（SOFC） cathode were evaluated by galvanostatic measurement. Comparison between two cathode materials was made to consider the cathode degradation mechanisms. The degradation performance is associated with a slow decomposition of the La0.6Sr0.4Co0.2Fe0.8O3（LSCF） due to the segregation of strontium oxide. Negligible deterioration for （La0.7Sr0.3）MnO3 （LSM） cathode was caused by SO2 poisoning under a current density of 200 mA/cm2. Metal sulphate formation may explain a slight deterioration under increasing high the concentration of SO2. It was verified that the poisoning mechanism for the two cathode materials resulted from the gradual decomposition of the cathode materials.
基金financially supported by the National Basic Research Program of China (Grant Nos. 2012CB215404, 2012CB215406)State Key Laboratory of Power Systems in Tsinghua University (No. SKLD15Z02, Fuel Cell Distributed Power Generation System)One-hundred Leading Talents Development Project for Progress on Science and Technology of Beijing (No. 041504130)
文摘Fluidized bed reactor is widely used in coal char-CO2 gasification. In this work, the production of syngas by using a fluidized bed gasification technique was first investigated and then the effect of the produced syngas on the performance of the solid oxide fuel cell with a configuration of La0.4Sr0.6Co0.2 Fe0.7 Nb0.1O3-δ//La0.8Sr0.2Ga0.83Mg0.17O3-δ//La0.4Sr0.6Co0.2Fe0.7Nb0.1O3-δ（LSCFN//LSGM//LSCFN） was studied. During the syngas production, we found that the volume fraction of CO increased with the increment of gasification temperature, and it reached a maximum value of 88.8%, corresponding to a composition of 0.76% H2, 88.8% CO, and 10.44% CO2, when the ratio of oxygen mass flow rate to that of coal char （Mo2/Mchar） increased to 0.29. In the following utilization of the produced syngas in solid oxide fuel cells, it was found that the increasing CO volume fraction in the syngas results in a gradual increase of the peak power density of the LSCFN//LSGM//LSCFN cell. The maximum peak power density of 410 mW/cm^2 was achieved for the syngas produced at 0.29 of Mo2/Mchar. In the stability test, the cell voltage decreased by 4% at a constant current density of 0.475 A/cm^2 after 54 h when fueled with the syngas with the composition of 0.76% H2, 88.8% CO, and 10.44% CO2. It reveals that a carbon deposition with the content of 13.66% in the anode is attributed to the cell performance degradation.
