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
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
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
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
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)~~
文摘化石燃料的使用排放了大量CO_2,对气候和环境造成了日益严重的危害.固体氧化物电解池(SOEC)能够利用可再生能源产生的电能将CO_2高效转化成CO,降低CO_2排放的同时,又能减少化石燃料的使用,近年来受到研究者的广泛关注.相比于低温液相CO_2电还原,SOEC高的运行温度保证了其较高的反应速率,即较高的电流密度.典型的SOEC单电池由多孔阴极、致密电解质和多孔阳极以三明治的方式组装而成.CO_2分子在阴极得到两个电子解离成CO和一个O_2^-;生成的O_2-通过致密电解质传导至阳极,在阳极失去四个电子发生析氧反应(OER)生成一个O_2.相比于两电子的阴极反应,阳极四电子的析氧反应更难进行,可能是整个电极过程的速控步,因此开发高性能的阳极材料有望显著提高SOEC的CO_2电还原性能.La_(0.6)Sr_(0.4)Co_(0.2)Fe_(0.8)O_(3-δ)(LSCF)因具有较高的混合离子-电子导电性而被用作SOEC阳极材料,但受LSCF-气体两相界面的限制,其OER性能较低.研究表明,LSCF-掺杂的Ce O2-气体所构成的三相界面相比于LSCF-气体两相界面具有更高的电化学反应活性,即OER反应更易在三相界面进行.因此,本文将Gd_(0.2)Ce_(0.8)O_(1.9)(GDC)纳米颗粒浸渍到SOEC LSCF阳极来提高其OER活性,考察了纳米颗粒浸渍量(3,5,10和20 wt%)对SOEC电化学性能的影响.结果表明,SOEC的电化学性能随浸渍量的增加而逐渐升高,当GDC纳米颗粒浸渍量为10 wt%时(10GDC/LSCF),SOEC的电化学性能达到最高,在800 oC和1.6V的电流密度为0.555 A cm^(-2),是LSCF阳极SOEC性能的1.32倍.继续增加浸渍量到20 wt%,电化学性能反而开始下降.电化学阻抗谱测试结果表明,GDC纳米颗粒的加入减小了SOEC的极化电阻.对应的弛豫时间分布函数解析结果表明10GDC/LSCF阳极上的OER由四个基元反应构成.电镜和O_2^-程序升温脱附结果表明,GDC纳米颗粒的加入显著增加了10GDC/LSCF阳极三相界面和表面氧空位的数量以及体相氧的流动性,从而促进了OER四个基元反应的反应速率,降低了这几个过程的极化电阻,因而降低了OER反应的极化电阻,提高了SOEC电还原CO2的电化学性能.
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。
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.
