Boosting oxygen reduction activity and CO_(2) resistance on bismuth ferrite-based perovskite cathode for low-temperature solid oxide fuel cells below 600℃

Developing efficient and stable cathodes for low-temperature solid oxide fuel cells(LT-SOFCs) is of great importance for the practical commercialization.Herein,we propose a series of Sm-modified Bi_(0.7-x)Sm_xSr_(0.3)FeO_(3-δ) perovskites as highly-active catalysts for LT-SOFCs.Sm doping can significantly enhance the electrocata lytic activity and chemical stability of cathode.At 600℃,Bi_(0.675)Sm_(0.025)Sr_(0.3)FeO_(3-δ)(BSSF25) cathode has been found to be the optimum composition with a polarization resistance of 0.098 Ω cm^2,which is only around 22.8% of Bi_(0.7)Sr_(0.3)FeO_(3-δ)(BSF).A full cell utilizing BSSF25 displays an exceptional output density of 790 mW cm^(-2),which can operate continuously over100 h without obvious degradation.The remarkable electrochemical performance observed can be attributed to the improved O_(2) transport kinetics,superior surface oxygen adsorption capacity,as well as O_(2)p band centers in close proximity to the Fermi level.Moreover,larger average bonding energy(ABE) and the presence of highly acidic Bi,Sm,and Fe ions restrict the adsorption of CO_(2) on the cathode surface,resulting in excellent CO_(2) resistivity.This work provides valuable guidance for systematic design of efficient and durable catalysts for LT-SOFCs.

Recent progresses in the development of tubular segmented-in-series solid oxide fuel cells:Experimental and numerical study

Solid oxide fuel cells(SOFCs)have attracted a great deal of interest because they have the highest efficiency without using any noble metal as catalysts among all the fuel cell technologies.However,traditional SOFCs suffer from having a higher volume,current leakage,complex connections,and difficulty in gas sealing.To solve these problems,Rolls-Royce has fabricated a simple design by stacking cells in series on an insulating porous support,resulting in the tubular segmented-in-series solid oxide fuel cells(SIS-SOFCs),which achieved higher output voltage.This work systematically reviews recent advances in the structures,preparation methods,perform-ances,and stability of tubular SIS-SOFCs in experimental and numerical studies.Finally,the challenges and future development of tubular SIS-SOFCs are also discussed.The findings of this work can help guide the direction and inspire innovation of future development in this field.

Lattice Boltzmann simulation study of anode degradation in solid oxide fuel cells during the initial aging process

For present solid oxide fuel cells(SOFCs),rapid performance degradation is observed in the initial aging process,and the dis-cussion of the degradation mechanism necessitates quantitative analysis.Herein,focused ion beam-scanning electron microscopy was em-ployed to characterize and reconstruct the ceramic microstructures of SOFC anodes.The lattice Boltzmann method(LBM)simulation of multiphysical and electrochemical processes in the reconstructed models was performed.Two samples collected from industrial-size cells were characterized,including a reduced reference cell and a cell with an initial aging process.Statistical parameters of the reconstructed microstructures revealed a significant decrease in the active triple-phase boundary and Ni connectivity in the aged cell compared with the reference cell.The LBM simulation revealed that activity degradation is dominant compared with microstructural degradation during the initial aging process,and the electrochemical reactions spread to the support layer in the aged cell.The microstructural and activity de-gradations are attributed to Ni migration and coarsening.

Effects of operating conditions on the performance degradation and anode microstructure evolution of anode-supported solid oxide fuel cells

Performance degradation shortens the life of solid oxide fuel cells in practical applications.Revealing the degradation mechanism is crucial for the continuous improvement of cell durability.In this work,the effects of cell operating conditions on the terminal voltage and anode microstructure of a Ni-yttria-stabilized zirconia anode-supported single cell were investigated.The microstructure of the anode active area near the electrolyte was characterized by laser optical microscopy and focused ion beam-scanning electron microscopy.Ni depletion at the anode/electrolyte interface region was observed after 100 h discharge tests.In addition,the long-term stability of the single cell was evaluated at 700℃for 3000 h.After an initial decline,the anode-supported single cell exhibits good durability with a voltage decay rate of 0.72%/kh and an electrode polarization resistance decay rate of 0.17%/kh.The main performance loss of the cell originates from the initial degradation.

Fabrication of Gd_(2)O_(3)-doped CeO_(2)thin films through DC reactive sputtering and their application in solid oxide fuel cells

Physical vapor deposition(PVD)can be used to produce high-quality Gd_(2)O_(3)-doped CeO2(GDC)films.Among various PVD methods,reactive sputtering provides unique benefits,such as high deposition rates and easy upscaling for industrial applications.GDC thin films were successfully fabricated through reactive sputtering using a Gd_(0.2)Ce_(0.8)(at%)metallic target,and their application in solid oxide fuel cells,such as buffer layers between yttria-stabilized zirconia(YSZ)/La0.6Sr0.4Co0.2Fe0.8O_(3−δ)and as sublayers in the steel/coating system,was evaluated.First,the direct current(DC)reactive-sputtering behavior of the GdCe metallic target was determined.Then,the GDC films were deposited on NiO-YSZ/YSZ half-cells to investigate the influence of oxygen flow rate on the quality of annealed GDC films.The results demonstrated that reactive sputtering can be used to prepare thin and dense GDC buffer layers without high-temperature sintering.Furthermore,the cells with a sputtered GDC buffer layer showed better electrochemical performance than those with a screen-printed GDC buffer layer.In addition,the insertion of a GDC sublayer between the SUS441 interconnects and the Mn-Co spinel coatings contributed to the reduction of the oxidation rate for SUS441 at operating temperatures,according to the area-specific resistance tests.

Recent advances and influencing parameters in developing electrode materials for symmetrical solid oxide fuel cells

This article delivers a robust overview of potential electrode materials for use in symmetrical solid oxide fuel cells(S-SOFCs),a relatively new SOFC technology.To this end,this article provides a comprehensive review of recent advances and progress in electrode materials for S-SOFC,discussing both the selection of materials and the challenges that come with making that choice.This article discussed the relevant factors involved in developing electrodes with nano/microstructure.Nanocomposites,e.g.,non-cobalt and lithiated materials,are only a few of the electrode types now being researched.Furthermore,the phase structure and microstructure of the produced materials are heavily influenced by the synthesis procedure.Insights into the possibilities and difficulties of the material are discussed.To achieve the desired microstructural features,this article focuses on a synthesis technique that is either the most recent or a better iteration of an existing process.The portion of this analysis that addresses the risks associated with manufacturing and the challenges posed by materials when fabricating S-SOFCs is the most critical.This article also provides important and useful recommendations for the strategic design of electrode materials researchers.

Low molecular weight alkane-fed solid oxide fuel cells for power and chemicals cogeneration

This paper presents a review of low molecular weight alkane-fed solid oxide fuel cells(SOFCs),which,unlikely the conventional use of SOFCs for only power production,are utilized to cogenerate produce useful chemicals at the same time.The cogeneration processes in SOFC have been classified according to the different types of fuel.C_(2)and C_(3)alkenes and synthesis gas are the main cogenerated chemicals together with electricity.The chemicals and energy cogeneration in a fuel cell reactor seems to be an effective alternative to conventional reactors for only chemicals production and conventional fuel cells for only power production.Although,the use of SOFCs for chemicals and energy cogeneration has proved successful in the industrial setting,the development of new catalysts aimed at obtaining the desired chemicals together with the production of a high amount of energy,and optimizing SOFC operation conditions is still a challenge to enhance system performance and make commercial applications workable.

Temperature Gradient Analyses of a Tubular Solid Oxide Fuel Cell Fueled by Methanol

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.

Interface engineering of an electrospun nanofiber-based composite cathode for intermediate-temperature solid oxide fuel cells

Sluggish oxygen reduction reaction(ORR)kinetics are a major obstacle to developing intermediate-temperature solid-oxide fuel cells(IT-SOFCs).In particular,engineering the anion defect concentration at an interface between the cathode and electrolyte is important for facilitating ORR kinetics and hence improving the electrochemical performance.We developed the yttria-stabilized zirconia(YSZ)nanofiber(NF)-based composite cathode,where the oxygen vacancy concentration is controlled by varying the dopant cation(Y2O3)ratio in the YSZ NFs.The composite cathode with the optimized oxygen vacancy concentration exhibits maximum power densities of 2.66 and 1.51 W cm^(−2)at 700 and 600℃,respectively,with excellent thermal stability at 700℃ over 500 h under 1.0 A cm^(−2).Electrochemical impedance spectroscopy and distribution of relaxation time analysis revealed that the high oxygen vacancy concentration in the NF-based scaffold facilitates the charge transfer and incorporation reaction occurred at the interfaces between the cathode and electrolyte.Our results demonstrate the high feasibility and potential of interface engineering for achieving IT-SOFCs with higher performance and stability.

Radio-frequency magnetron sputtered thin-film La_(0.5)Sr_(0.5)Co_(0.95)Nb_(0.05)O_(3-δ) perovskite electrodes for intermediate temperature symmetric solid oxide fuel cell(IT-SSOFC)

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.

Future development of solid oxide fuel cell

Solid oxide fuel cell(SOFC) technology and its status and problems were briefly described.Several topics for furtherresearch and development were proposed.

Plasma-Sprayed Coating of an Apatite-Type Lanthanum Silicate Electrolyte for Intermediate Temperature Solid Oxide Fuel Cells (IT-SOFCs)

Apatite-type lanthanum silicate was successfully synthesized via a solid state re- action protocol at 1400~C in a vacuum for 4 hours. The powder was synthesized faster and at a lower reaction temperature than by conventional solid state reaction methods. The resulting powder was used in the fabrication of a coating deposited by atmospheric plasma spray （APS） technology. The microstructure of the coating was analyzed by X-ray diffraction and scanning electron microscopy. Heat treatment was found to fully crystallize the coating, increasing its den-sity. The ionic conductivity of the apatite coating was 0.39 （0.054） mS/cm at 850 （700） ℃, and its activation energy was 0.67 eV.

Measuring Porosity of Anodes in Solid Oxide Fuel Cell (SOFC) through Water Archimedeans Porosimetry

The present research is aimed to measure the porosity of anodes in solid oxide fuel cell through water Archimedeans method. There are various alternatives available to replace fossil fuel cells like nuclear power, wind energy, solar energy, bio fuel, and geothermal and fuel cells. Among all the alternatives of fossil fuel, one form of energy production that stands out from the rest and promises a sustainable future energy is fuel cell. Moreover, it offers many advantages in contrast to other forms of energy generation. An Archimedean approach for water immersion porosimetry is carried out. Some of the results are beyond rational limits, and given negative and sometime above 100 percent porosity. The reasons for these unacceptable results are either due to water ingress into the sample or the sample turns into buoyant due to air in the cling film. The results from Archimedean porosimetry should only be used qualitatively due to errors associated with the results. It is also noted that Archimedean porosimetry is not the ideal technique for measuring the porosity of coated samples. It is suggested that larger samples should be analyzed that will help to minimize the weighing errors.

Progress and challenges of carbon-fueled solid oxide fuel cells anode

Carbon-fueled solid oxide fuel cells(CF-SOFCs)can electrochemically convert the chemical energy in carbon into electricity,which demonstrate both superior electrical efficiency and fuel utilisation compared to all other types of fuel cells.However,using solid carbon as the fuel of SOFCs also faces some challenges,the fluid mobility and reactive activity of carbon-based fuels are much lower than those of gaseous fuels.Therefore,the anode reaction kinetics plays a crucial role in determining the electrochemical performance of CF-SOFCs.Herein,the progress of various anodes in CF-SOFCs is reviewed from the perspective of material compositions,electrochemical performance and microstructures.Challenges faced in developing high performance anodes for CF-SOFCs are also discussed.

Preparation and Characterization of Component Materials for Intermediate Temperature Solid Oxide Fuel Cell by Glycine-Nitrate Process

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.

Solid oxide fuel cells in combination with biomass gasification for electric power generation

Biomass,a source of renewable energy,represents an effective substitute to fossil fuels.Gasification is a process that organics are thermochemically converted into valuable gaseous products(e.g.biogas).In this work,the catalytic test demonstrated that the biogas produced from biomass gasification mainly consists of H2,CH4,CO,and CO2,which were then be used as the fuel for solid oxide fuel cell(SOFC).Planar SOFCs were fabricated and adopted.The steam reforming of biogas was carried out at the anode of a SOFC to obtain a hydrogen-rich fuel.The performance of the SOFCs operating on generated biogas was investigated by I-V polarization and electrochemical impedance spectra characterizations.An excellent cell performance was obtained,for example,the peak power density of the SOFC reached 1391 mW·cm-2 at 750℃when the generated biogas was used as the fuel.Furthermore,the SOFC fuelled by simulated biogas delivered a very stable operation.

Modelling of a tubular solid oxide fuel cell with different designs of indirect internal reformer

The cell performance and temperature gradient of a tubular solid oxide fuel cell with indirect internal reformer （IIR-SOFC） fuelled by natural gas, containing a typical catalytic packed-bed reformer, a catalytic coated wall reformer, a catalytic annular reformer, and a novel catalytic annular-coated wall reformer were investigated with an aim to determine the most efficient internal reformer system. Among the four reformer designs, IIR-SOFC containing an annular-coated wall reformer exhibited the highest performance in terms of cell power density （0.67 W.cm 2） and electrical efficiency （68%） with an acceptable temperature gradient and a moderate pressure drop across the reformer （3.53 × 10 5 kPa）. IIR-SOFC with an annular-coated wall reformer was then studied over a range of operating conditions： inlet fuel temperature, operating pressure, steam to carbon （S ： C） ratio, gas flow pattern （co-flow and counter-flow pattern）, and natural gas compositions. The simulation results showed that the temperature gradient across the reformer could not be decreased using a lower fuel inlet temperature （1223 K-1173 K） and both the power density and electrical efficiency of the cell also decreased by lowering fuel inlet temperature. Operating in higher pressure mode （1-10 bar） improved the temperature gradient and cell performance. Increasing the S ： C ratio from 2 ： 1 to 4：1 could decrease the temperature drop across the reformer but also decrease the cell performance. The average temperature gradient was higher and smoother in IIR-SOFC under a co-flow pattern than that under a counter-flow pattern, leading to lower overpotential and higher cell performance. Natural gas compositions significantly affected the cell performance and temperature gradient. Natural gas containing lower methane content provided smoother temperature gradient in the system but showed lower power density and electrical efficiency.

Sealing Glass of Barium-Calcium-Aluminosilicate System for Solid Oxide Fuel Cells

Glass-ceramic materials were developed as a sealant in the solid oxide fuel cell （SOFC） in the temperature range of 800 -850 ℃. The glass materials were based on the glass and glass-ceramic in the BaO-CaO-Al2O3-SiO2-La2O3-B2O3 system. The thermal expansion coefficient （TEC） decreased with lower Ba^2＋ content and higher Ca^2＋ content, but the glass transition temperature and crystallization temperature increased greatly with an increase in Ca^2＋ content and a decrease in Ba^2＋ content, when the other components in the sealant were invariable. The TEC of the sealant with Ba^2＋ content of 25.4% was 10.8 × 10^-6 K^- 1（temperature range from 25 to 850℃）, and its softening temperature was 950 ℃. The TEC of the sealant accorded well with that of La0.9Sr0.1Ga0.5Mg0.2o3- 6（LSGM） with a mismatch of only 3%. The sealant had superior stability and compatibility with the LSGM electrolyte during the process of operation in SOFC. The weight loss of the sealant with Ba^2＋ content of 25.4% was approfimately zero after heat-treated at 800℃ for 500 h in H2 and O2 atmosphere, respectively.

LSM-infiltrated LSCF cathodes for solid oxide fuel cells

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.

Effect of H_2S Flow Rate and Concentration on Performance of H_2S/Air Solid Oxide Fuel Cell

A solid state H2S/air electrochemical cell having the configuration of H2S, (MoS2+NiS+Ag)/YSZ/Pt,air has been examined with different H2S flow rates and concentrations at atmospheric pressure and 750-850℃.Performance of the fuel cell was dependent on anode compartment H2S flow rate and concentration. The cell open-circuit voltage increased with increasing H2S flow rate. It was found that increasing both H2S flow rate and H2S concentration improved current-voltage and power density performance. This is resulted from improved gas diffusion in anode and increased concentration of anodic electroactive species. Operation at elevated H2S concentration improved the cell performance at a given gas flow rate. However, as low as 5% H2S in gas mixture can also be utilized as fuel feed to cells. Highest current and power densities, 1750mA·cm^-2 and 200mW·cm^-2,are obtained with pure H2S flow rate of 50 ml·min^-1 and air flow rate of 100ml·min^-1 at 850℃.