Compared with conventional electric power generation systems, the solid oxide fuel cell （SOFC） has many advantages because of its unique features. High temperature SOFC has been successfully developed to its commerc...Compared with conventional electric power generation systems, the solid oxide fuel cell （SOFC） has many advantages because of its unique features. High temperature SOFC has been successfully developed to its commercial applications, but it still faces many problems which hamper large-scale commercial applications of SOFC. To reduce the cost of SOFC, intermediate temperature solid oxide fuel cell （IT-SOFC） is presently under rapid development. The status of IT-SOFC was reviewed with emphasis on discussion of their component materials. 2008 University of Science and Technology Beijing. All rights reserved.展开更多
Thermal management in solid oxide fuel cells(SOFC)is a critical issue due to non-uniform electrochemical reactions and convective fl ows within the cells.Therefore,a 2D mathematical model is established herein to inve...Thermal management in solid oxide fuel cells(SOFC)is a critical issue due to non-uniform electrochemical reactions and convective fl ows within the cells.Therefore,a 2D mathematical model is established herein to investigate the thermal responses of a tubular methanol-fueled SOFC.Results show that unlike the low-temperature condition of 873 K,where the peak temperature gradient occurs at the cell center,it appears near the fuel inlet at 1073 K because of the rapid temperature rise induced by the elevated current density.Despite the large heat convection capacity,excessive air could not eff ectively eliminate the harmful temperature gradient caused by the large current density.Thus,optimal control of the current density by properly selecting the operating potential could generate a local thermal neutral state.Interestingly,the maximum axial temperature gradient could be reduced by about 18%at 973 K and 20%at 1073 K when the air with a 5 K higher temperature is supplied.Additionally,despite the higher electrochemical performance observed,the cell with a counter-fl ow arrange-ment featured by a larger hot area and higher maximum temperature gradients is not preferable for a ceramic SOFC system considering thermal durability.Overall,this study could provide insightful thermal information for the operating condition selection,structure design,and stability assessment of realistic SOFCs combined with their internal reforming process.展开更多
La1-xSrxGa1-y MgyO3-δ(LSGM) electrolyte, La1-xSrxCr1-y MnyO3-δ( LSCM ) anode and La1-xSrxFe1-y MnyO3-aaaaaaa(LSFM) cathode materials were all synthesized by glycine-nitrate process (GNP). The microstructure and char...La1-xSrxGa1-y MgyO3-δ(LSGM) electrolyte, La1-xSrxCr1-y MnyO3-δ( LSCM ) anode and La1-xSrxFe1-y MnyO3-aaaaaaa(LSFM) cathode materials were all synthesized by glycine-nitrate process (GNP). The microstructure and characteristics of LSGM, LSCM and LSFM were tested via X-ray diffraction(XRD), scanning electron microcopy (SEM), A C impedance and four-probe direct current techniques. XRD shows that pure perovskite phase LSGM electrolyte and electrode (LSCM anode and LSFM cathode) materials were prepared after being sintered at 1400℃for 20 h and at 1000℃for 5 h, respectively. The max conductivities of LSGM (ionic conductivity), LSCM (total conductivity) and LSFM (total conductivity) materials are 0.02, 10, 16 S·cm-1 in the air below 850℃, respectively. The conductivity of LSCM becomes smaller when the atmosphere changes from air to pure hydrogen at the same temperature and it decreases with the temperature like metal. The porous and LSGM-based LSCM anode and LSFM cathode films were prepared by screen printing method, and the sintering temperatures for them were 1300 and 1250℃, respectively. LSGM and electrode (LSCM and LSFM) materials have good thermal and chemical compatibility.展开更多
La1-xSrxCr1-yMnyO3-δ(LSCM) anode materials were synthesized by glycine nitrate process(GNP). Thermo-gravimetric analysis(TGA) and differential scanning calorimetric(DSC) methods were adopted to investigate the reacti...La1-xSrxCr1-yMnyO3-δ(LSCM) anode materials were synthesized by glycine nitrate process(GNP). Thermo-gravimetric analysis(TGA) and differential scanning calorimetric(DSC) methods were adopted to investigate the reaction process of LSCM anode materials. The oxides prepared were characterized via X-ray diffraction(XRD),scanning electron microscope and energy dispersive spectroscopy(SEM-EDS),direct current four-electrode and temperature process reduction(TPR) techniques. XRD patterns indicate that perovskite phase created after the precursor was sintered at 1 000 ℃ for 5 h,and single perovskite-type oxides formed after the precursor were sintered at 1 200 ℃ for 5 h. The powders are micrometer size after sintering at 1 000 ℃ and 1 200 ℃,respectively. The conductivities of LSCM samples increase linearly with increasing the temperature from 250 ℃ to 850 ℃ in air and the maximum value is 32 S/cm for La0.7Sr0.3Cr0.5Mn0.5O3-δ. But it is lower about two orders of magnitude in pure hydrogen or methane than that of the same sample in the air. TPR result indicates that LSCM offers excellently catalytic performance.展开更多
The present work explores the application of La_(0.5)Sr_(0.5)Co_(0.95)Nb_(0.05)O_(3-δ)(LSCNO)perovskite as electrode material for the symmetric solid oxide fuel cell.Symmetric solid oxide fuel cells of thin-film LSCN...The present work explores the application of La_(0.5)Sr_(0.5)Co_(0.95)Nb_(0.05)O_(3-δ)(LSCNO)perovskite as electrode material for the symmetric solid oxide fuel cell.Symmetric solid oxide fuel cells of thin-film LSCNO electrodes were prepared to study the oxygen reduction reaction at intermediate temperature.The Rietveld refinement of syn-thesized material shows a hexagonal structure with the R-3c space group of the prepared perovskite material.Lattice parameter and fractional coordinates were utilized to calculate the oxygen ion diffusion coefficient for molecular dynamic simulation.At 973 K,the oxygen ion diffusion of LSCNO was 1.407×10^(-8)cm^(2)s^(-1) higher by order of one magnitude than that of the La_(0.5)Sr_(0.5)Co_(0.95)Nb_(0.05)O_(3-δ)(7.751×10^(-9)cm^(2)^(-1)).The results suggest that the Nb doping provide the structural stability which improves oxygen anion diffusion.The enhanced structural stability was analysed by the thermal expansion coefficient calculated experimentally and from molecular dynamics simulations.Furthermore,the density functional theory calculation revealed the role of Nb dopant for oxygen vacancy formation energy at Sr-0 and La-O planes is lower than the undoped structure.To understand the rate-limiting process for sluggish oxygen diffusion kinetics,80 nm and 40 nm thin films were fabricated using radio frequency magnetron sputtering on gadolinium doped ceria electrolyte substrate.The impedance was observed to increase with an increasing thickness,suggesting the bulk diffusion as a rate-limiting step for oxygen ion diffu-sion.The electrochemical performance was analysed for the thin-flm symmetric solid oxide fuel cell,which achieved a peak power density of 390 mW cm^(-2) at 1.02 V in the presence of H_(2) fuel on the anode side and air on the cathode side.展开更多
High temperature solid oxide fuel cell(SOFC)is the most efficient and clean energy conversion technology to electrochemically convert the chemical energy of fuels such as hydrogen,natural gas and hydrocarbons to elect...High temperature solid oxide fuel cell(SOFC)is the most efficient and clean energy conversion technology to electrochemically convert the chemical energy of fuels such as hydrogen,natural gas and hydrocarbons to electricity,and also the most viable alternative to the traditional thermal power plants.However,the power output of a SOFC critically depends on the characteristics and performance of its key components:anode,electrolyte and cathode.Due to the highly reducing environment and strict requirements in electrical conductivity and catalytic activity,there are limited choices in the anode materials of SOFCs,particularly for operation in the intermediate temperature range of 500–800C.Among them,Ni-based cermets are the most common and popular anode materials of SOFCs.The objective of this paper is to review the development of Ni-based anode materials in SOFC from the viewpoints of materials microstructure,performance and industrial scalability associated with the fabrication and optimization processes.The latest advancement in nano-structure architecture,contaminant tolerance and interface optimization of Ni-based cermet anodes is presented.And at the end of this paper,we propose and appeal for the collaborative work of scientists from different disciplines that enable the inter-fusion research of fabrication,microanalysis and modelling,aiming at the challenges in the development of Ni-based cermet anodes for commercially viable intermediate temperature SOFC or IT-SOFC technologies.展开更多
New cobalt-free composites consisting of Ba0.5Sr0.5Fe0.9Ni0.1O3-δ （BSFN） and Ce0.8Sm0.2O2-δ （SDC） were investigated as possible cathode materials for intermediate-temperature solid oxide fuel cell （IT-SOFC）. B...New cobalt-free composites consisting of Ba0.5Sr0.5Fe0.9Ni0.1O3-δ （BSFN） and Ce0.8Sm0.2O2-δ （SDC） were investigated as possible cathode materials for intermediate-temperature solid oxide fuel cell （IT-SOFC）. BSFN, which was synthesized by auto ignition process, was chemically compatible with SDC up to 1100 ℃ as indicated by X-ray diffraction analysis. The electrical conductivity of BSFN reached the maximum value of 57 S.cm-1 at 450 ℃. The thermal expansion coefficient （TEC） value of BSFN was 30.9×10-6 K-1, much higher than that of typical electrolytes. The electrochemical behavior of the composites was analyzed via electrochemical impedance spectroscopy with symmetrical cells BSFN-SDC/SDC/BSFN-SDC. The area specific interracial polarization resistance （ASR） decreased with increasing SDC content of the composite. The area specific interracial polarization resistance （ASR） at 700 ℃ is only 0.49, 0.34 and 0.31 Ω.cm2 when 30, 40, and 50 wt% SDC was cooperated to BSFN, respectively. These results suggest that BSFN-SDC is a possible candidate for IT-SOFC cathode.展开更多
One of the major challenges to develop "intermediate temperature" solid oxide fuel cells is finding a novel cathode material, which can meet the following requirements: (1) high electronic conductivity; (2) ...One of the major challenges to develop "intermediate temperature" solid oxide fuel cells is finding a novel cathode material, which can meet the following requirements: (1) high electronic conductivity; (2) chemical compatibility with the electrolyte; (3) a matched thermal expansion coefficient (TEC); (4) stability in a wide range of oxygen partial pressure; and (5) high catalytic activity for the oxygen reduction reaction (ORR). In this short review, a survey of these requirements for K2NiF4-type material with the formula Ln2MO4, Ln = La, Pr, Nd, Sm; M = Ni, Cu, Fe, Co, Mn, is presented. The composition-dependent TEC, electrical conductivity and oxygen transport property are considered. The Ln2MO4 materials exhibit improved chemical stability and compatibility with most of the traditional electrolytes. The complete fuel cells integrated with Ln2MO4 materials as cathodes show promising results. Furthermore, these materials are considered as cathodes of protonic ceramic fuel cell (PCFC), and/or anodes of high temperature steam electrolysis (HTSE). First results show excellent performances. The versatility of these Ln2MO4 materials is explained on the basis of structural features and the ability to accommodate oxygen non-stoichiometry.展开更多
The precursors of La0.7Sr0.3-xCaxCo0.9Fe0.1O3-δ(LSCCF, x=0.05, 0.10, 0.15, 0.20) as the cathode materials for intermediate temperature solid oxide fuel cell (ITSOFC) were prepared by reverse titration co-precipitatio...The precursors of La0.7Sr0.3-xCaxCo0.9Fe0.1O3-δ(LSCCF, x=0.05, 0.10, 0.15, 0.20) as the cathode materials for intermediate temperature solid oxide fuel cell (ITSOFC) were prepared by reverse titration co-precipitation method with metal-nitrates as starting materials and mixed alkali (NaOH and Na2CO3) as a precipitating agent. The formation process of LSCCF from the precursors was monitored by TG-DSC, and the crystal structure and particles morphology of the precursors which were calcined at 600, 800, 1000 ℃ for 3 h were characterized using XRD, SEM technologies. Compared with the solid state reaction of constituent oxides, when the pH value of the precipitating solution was in the range of 9.1～9.5, the LSCCF powders from the precursors caclined at 800 ℃ for 3 h had high purity, homogeneous and single perovskite phase. The electrical conductivity of the LSCCF samples sintered at 1200 ℃ for 3 h, which was measured as a function of temperatures from 100 to 800 ℃ by DC four-probe method in air, decreased with x from 0.05 to 0.20. The value of electrical conductivity was almost equal because of Ca2+, Sr2+ co-dopant resulting in the 'mix effect' while x=0.10 or 0.15. The electrical conductivity of all doped samples was higher than 100 S·cm-1 at intermediate temperatures from 500 to 800 ℃, and there was good compatibility between the LSCCF cathode and Ce0.8Sm0.2O2 electrolyte.展开更多
基金the National Basic Research Program of China(No.2007CB936201)the National High Technology Research and Development Program of China(863 Program)(No.2006AAO3Z351)the Major International(Regional)Joint Research Program of China(No.50620120439,2006DFB51000).
文摘Compared with conventional electric power generation systems, the solid oxide fuel cell （SOFC） has many advantages because of its unique features. High temperature SOFC has been successfully developed to its commercial applications, but it still faces many problems which hamper large-scale commercial applications of SOFC. To reduce the cost of SOFC, intermediate temperature solid oxide fuel cell （IT-SOFC） is presently under rapid development. The status of IT-SOFC was reviewed with emphasis on discussion of their component materials. 2008 University of Science and Technology Beijing. All rights reserved.
基金by the Project of Strategic Importance Funding Scheme from The Hong Kong China Polytechnic University(No.P0035168)the National Natural Science Foundation of China(No.51806241).
文摘Thermal management in solid oxide fuel cells(SOFC)is a critical issue due to non-uniform electrochemical reactions and convective fl ows within the cells.Therefore,a 2D mathematical model is established herein to investigate the thermal responses of a tubular methanol-fueled SOFC.Results show that unlike the low-temperature condition of 873 K,where the peak temperature gradient occurs at the cell center,it appears near the fuel inlet at 1073 K because of the rapid temperature rise induced by the elevated current density.Despite the large heat convection capacity,excessive air could not eff ectively eliminate the harmful temperature gradient caused by the large current density.Thus,optimal control of the current density by properly selecting the operating potential could generate a local thermal neutral state.Interestingly,the maximum axial temperature gradient could be reduced by about 18%at 973 K and 20%at 1073 K when the air with a 5 K higher temperature is supplied.Additionally,despite the higher electrochemical performance observed,the cell with a counter-fl ow arrange-ment featured by a larger hot area and higher maximum temperature gradients is not preferable for a ceramic SOFC system considering thermal durability.Overall,this study could provide insightful thermal information for the operating condition selection,structure design,and stability assessment of realistic SOFCs combined with their internal reforming process.
基金Project supported by the National Natural Science Foundation of China (50204007)the Foundation of Yunnan Province (2005PY01-33)
文摘La1-xSrxGa1-y MgyO3-δ(LSGM) electrolyte, La1-xSrxCr1-y MnyO3-δ( LSCM ) anode and La1-xSrxFe1-y MnyO3-aaaaaaa(LSFM) cathode materials were all synthesized by glycine-nitrate process (GNP). The microstructure and characteristics of LSGM, LSCM and LSFM were tested via X-ray diffraction(XRD), scanning electron microcopy (SEM), A C impedance and four-probe direct current techniques. XRD shows that pure perovskite phase LSGM electrolyte and electrode (LSCM anode and LSFM cathode) materials were prepared after being sintered at 1400℃for 20 h and at 1000℃for 5 h, respectively. The max conductivities of LSGM (ionic conductivity), LSCM (total conductivity) and LSFM (total conductivity) materials are 0.02, 10, 16 S·cm-1 in the air below 850℃, respectively. The conductivity of LSCM becomes smaller when the atmosphere changes from air to pure hydrogen at the same temperature and it decreases with the temperature like metal. The porous and LSGM-based LSCM anode and LSFM cathode films were prepared by screen printing method, and the sintering temperatures for them were 1300 and 1250℃, respectively. LSGM and electrode (LSCM and LSFM) materials have good thermal and chemical compatibility.
基金Project(50204007) supported by the National Natural Science Foundation of ChinaProject(2005PY01-33) supported by the Talent Foundation of Yunnan Province, China
文摘La1-xSrxCr1-yMnyO3-δ(LSCM) anode materials were synthesized by glycine nitrate process(GNP). Thermo-gravimetric analysis(TGA) and differential scanning calorimetric(DSC) methods were adopted to investigate the reaction process of LSCM anode materials. The oxides prepared were characterized via X-ray diffraction(XRD),scanning electron microscope and energy dispersive spectroscopy(SEM-EDS),direct current four-electrode and temperature process reduction(TPR) techniques. XRD patterns indicate that perovskite phase created after the precursor was sintered at 1 000 ℃ for 5 h,and single perovskite-type oxides formed after the precursor were sintered at 1 200 ℃ for 5 h. The powders are micrometer size after sintering at 1 000 ℃ and 1 200 ℃,respectively. The conductivities of LSCM samples increase linearly with increasing the temperature from 250 ℃ to 850 ℃ in air and the maximum value is 32 S/cm for La0.7Sr0.3Cr0.5Mn0.5O3-δ. But it is lower about two orders of magnitude in pure hydrogen or methane than that of the same sample in the air. TPR result indicates that LSCM offers excellently catalytic performance.
文摘The present work explores the application of La_(0.5)Sr_(0.5)Co_(0.95)Nb_(0.05)O_(3-δ)(LSCNO)perovskite as electrode material for the symmetric solid oxide fuel cell.Symmetric solid oxide fuel cells of thin-film LSCNO electrodes were prepared to study the oxygen reduction reaction at intermediate temperature.The Rietveld refinement of syn-thesized material shows a hexagonal structure with the R-3c space group of the prepared perovskite material.Lattice parameter and fractional coordinates were utilized to calculate the oxygen ion diffusion coefficient for molecular dynamic simulation.At 973 K,the oxygen ion diffusion of LSCNO was 1.407×10^(-8)cm^(2)s^(-1) higher by order of one magnitude than that of the La_(0.5)Sr_(0.5)Co_(0.95)Nb_(0.05)O_(3-δ)(7.751×10^(-9)cm^(2)^(-1)).The results suggest that the Nb doping provide the structural stability which improves oxygen anion diffusion.The enhanced structural stability was analysed by the thermal expansion coefficient calculated experimentally and from molecular dynamics simulations.Furthermore,the density functional theory calculation revealed the role of Nb dopant for oxygen vacancy formation energy at Sr-0 and La-O planes is lower than the undoped structure.To understand the rate-limiting process for sluggish oxygen diffusion kinetics,80 nm and 40 nm thin films were fabricated using radio frequency magnetron sputtering on gadolinium doped ceria electrolyte substrate.The impedance was observed to increase with an increasing thickness,suggesting the bulk diffusion as a rate-limiting step for oxygen ion diffu-sion.The electrochemical performance was analysed for the thin-flm symmetric solid oxide fuel cell,which achieved a peak power density of 390 mW cm^(-2) at 1.02 V in the presence of H_(2) fuel on the anode side and air on the cathode side.
基金This project was supported by Australian Research Council(DP180100731,DP 180100568)JSPS Joint Research Project(Open Partnership)under bilateral program between Japan and Australia(FY 2019-FY2020,DG 1270).
文摘High temperature solid oxide fuel cell(SOFC)is the most efficient and clean energy conversion technology to electrochemically convert the chemical energy of fuels such as hydrogen,natural gas and hydrocarbons to electricity,and also the most viable alternative to the traditional thermal power plants.However,the power output of a SOFC critically depends on the characteristics and performance of its key components:anode,electrolyte and cathode.Due to the highly reducing environment and strict requirements in electrical conductivity and catalytic activity,there are limited choices in the anode materials of SOFCs,particularly for operation in the intermediate temperature range of 500–800C.Among them,Ni-based cermets are the most common and popular anode materials of SOFCs.The objective of this paper is to review the development of Ni-based anode materials in SOFC from the viewpoints of materials microstructure,performance and industrial scalability associated with the fabrication and optimization processes.The latest advancement in nano-structure architecture,contaminant tolerance and interface optimization of Ni-based cermet anodes is presented.And at the end of this paper,we propose and appeal for the collaborative work of scientists from different disciplines that enable the inter-fusion research of fabrication,microanalysis and modelling,aiming at the challenges in the development of Ni-based cermet anodes for commercially viable intermediate temperature SOFC or IT-SOFC technologies.
文摘New cobalt-free composites consisting of Ba0.5Sr0.5Fe0.9Ni0.1O3-δ （BSFN） and Ce0.8Sm0.2O2-δ （SDC） were investigated as possible cathode materials for intermediate-temperature solid oxide fuel cell （IT-SOFC）. BSFN, which was synthesized by auto ignition process, was chemically compatible with SDC up to 1100 ℃ as indicated by X-ray diffraction analysis. The electrical conductivity of BSFN reached the maximum value of 57 S.cm-1 at 450 ℃. The thermal expansion coefficient （TEC） value of BSFN was 30.9×10-6 K-1, much higher than that of typical electrolytes. The electrochemical behavior of the composites was analyzed via electrochemical impedance spectroscopy with symmetrical cells BSFN-SDC/SDC/BSFN-SDC. The area specific interracial polarization resistance （ASR） decreased with increasing SDC content of the composite. The area specific interracial polarization resistance （ASR） at 700 ℃ is only 0.49, 0.34 and 0.31 Ω.cm2 when 30, 40, and 50 wt% SDC was cooperated to BSFN, respectively. These results suggest that BSFN-SDC is a possible candidate for IT-SOFC cathode.
基金supported by the National Natural Science Foundation of China (51072048)Research Project of New Century Excellent Talents in University (NCET-06-0349)Heilongjiang Educational Department (GZ09A204, 1152G027, 11531274 & 11531285)
文摘One of the major challenges to develop "intermediate temperature" solid oxide fuel cells is finding a novel cathode material, which can meet the following requirements: (1) high electronic conductivity; (2) chemical compatibility with the electrolyte; (3) a matched thermal expansion coefficient (TEC); (4) stability in a wide range of oxygen partial pressure; and (5) high catalytic activity for the oxygen reduction reaction (ORR). In this short review, a survey of these requirements for K2NiF4-type material with the formula Ln2MO4, Ln = La, Pr, Nd, Sm; M = Ni, Cu, Fe, Co, Mn, is presented. The composition-dependent TEC, electrical conductivity and oxygen transport property are considered. The Ln2MO4 materials exhibit improved chemical stability and compatibility with most of the traditional electrolytes. The complete fuel cells integrated with Ln2MO4 materials as cathodes show promising results. Furthermore, these materials are considered as cathodes of protonic ceramic fuel cell (PCFC), and/or anodes of high temperature steam electrolysis (HTSE). First results show excellent performances. The versatility of these Ln2MO4 materials is explained on the basis of structural features and the ability to accommodate oxygen non-stoichiometry.
基金the National High-Tech Development Plan (2006AA05Z417)the Natural Science Foundation of Lia-oning Province (20062145)the Education department of Liaoning Province (05L073)
文摘The precursors of La0.7Sr0.3-xCaxCo0.9Fe0.1O3-δ(LSCCF, x=0.05, 0.10, 0.15, 0.20) as the cathode materials for intermediate temperature solid oxide fuel cell (ITSOFC) were prepared by reverse titration co-precipitation method with metal-nitrates as starting materials and mixed alkali (NaOH and Na2CO3) as a precipitating agent. The formation process of LSCCF from the precursors was monitored by TG-DSC, and the crystal structure and particles morphology of the precursors which were calcined at 600, 800, 1000 ℃ for 3 h were characterized using XRD, SEM technologies. Compared with the solid state reaction of constituent oxides, when the pH value of the precipitating solution was in the range of 9.1～9.5, the LSCCF powders from the precursors caclined at 800 ℃ for 3 h had high purity, homogeneous and single perovskite phase. The electrical conductivity of the LSCCF samples sintered at 1200 ℃ for 3 h, which was measured as a function of temperatures from 100 to 800 ℃ by DC four-probe method in air, decreased with x from 0.05 to 0.20. The value of electrical conductivity was almost equal because of Ca2+, Sr2+ co-dopant resulting in the 'mix effect' while x=0.10 or 0.15. The electrical conductivity of all doped samples was higher than 100 S·cm-1 at intermediate temperatures from 500 to 800 ℃, and there was good compatibility between the LSCCF cathode and Ce0.8Sm0.2O2 electrolyte.
