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.

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.

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.

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.

From concept to commercialization:A review of tubular solid oxide fuel cell technology

The reduced sealing difficulty of tubular solid oxide fuel cells(SOFCs)makes the stacking of tubular cell groups relatively easy,and the thermal stress constraints during stack operation are smaller,which helps the stack to operate stably for a long time.The special design of tubular SOFC structures can completely solve the problem of high-temperature sealing,especially in the design of multiple single-cell series integrated into one tube,where each cell tube is equivalent to a small electric stack,with unique characteristics of high voltage and low current output,which can significantly reduce the ohmic polarization loss of tubular cells.This paper provides an overview of typical tubular SOFC structural designs both domestically and internationally.Based on the geometric structure of tubular SOFCs,they can be divided into bamboo tubes,bamboo flat tubes,single-section tubes,and single-section flat tube structures.Meanwhile,this article provides an overview of commonly used materials and preparation methods for tubular SOFCs,including commonly used materials and preparation methods for support and functional layers,as well as a comparison of commonly used preparation methods for microtubule SOFCs,It introduced the three most important parts of building a fuel cell stack:manifold,current collector,and ceramic adhesive,and also provided a detailed introduction to the power generation systems of different tubular SOFCs,Finally,the development prospects of tubular SOFCs were discussed.

Investigation and optimization of high-valent Ta-doped SrFeO_(3-δ)as air electrode for intermediate-temperature solid oxide fuel cells

To explore highly active and thermomechanical stable air electrodes for intermediate-temperature solid oxide fuel cells(ITSOFCs),10mol%Ta5+doped in the B site of strontium ferrite perovskite oxide(SrTa_(0.1)Fe_(0.9)O_(3-δ),STF)is investigated and optimized.The effects of Ta^(5+)doping on structure,transition metal reduction,oxygen nonstoichiometry,thermal expansion,and electrical performance are evaluated systematically.Via 10mol%Ta^(5+)doping,the thermal expansion coefficient(TEC)decreased from 34.1×10^(-6)(SrFeO_(3-δ))to 14.6×10^(-6) K^(-1)(STF),which is near the TEC of electrolyte(13.3×10^(-6) K^(-1) for Sm_(0.2)Ce_(0.8)O_(1.9),SDC),indicates excellent thermomechanical compatibility.At 550-750℃,STF shows superior oxygen vacancy concentrations(0.262 to 0.331),which is critical in the oxygen-reduction reaction(ORR).Oxygen temperature-programmed desorption(O_(2)-TPD)indicated the thermal reduction onset temperature of iron ion is around 420℃,which matched well with the inflection points on the thermos-gravimetric analysis and electrical conductivity curves.At 600℃,the STF electrode shows area-specific resistance(ASR)of 0.152Ω·cm^(2) and peak power density(PPD)of 749 mW·cm^(-2).ORR activity of STF was further improved by introducing 30wt%Sm_(0.2)Ce_(0.8)O_(1.9)(SDC)powder,STF+SDC composite cathode achieving outstanding ASR value of 0.115Ω·cm2 at 600℃,even comparable with benchmark cobalt-containing cathode,Ba_(0.5)Sr_(0.5)Co_(0.8)Fe_(0.2)O_(3-δ)(BSCF).Distribution of relaxation time(DRT)analysis revealed that the oxygen surface exchange and bulk diffusion were improved by forming a composite cathode.At 650℃,STF+SDC composite cathode achieving an outstanding PPD of 1117 mW·cm^(-2).The excellent results suggest that STF and STF+SDC are promising air electrodes for IT-SOFCs.

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.

Novel synthesis of stabilized Bi_(1-x-y)Gd_(x)Dy_(y)O_(1.5) solid electrolytes with enhanced conductivity for intermediate temperature solid oxide fuel cells(SOFCs)

Herein,we report the synthesis of a Dy-Gd co-doped cubic phase-stabilized Bi_(2)O_(3) solid electrolyte system via solid-state processing under atmospheric conditions.Doping with Dy^(3+) and Gd^(3+) has been observed to significantly enhance the densification process during sintering for stabilization purposes,thereby improving the electrical properties of δ-Bi_(2)O_(3)-type polymorphs.The synthesized ceramics were characterized using X-ray diffraction(XRD),field emission scanning electron microscopy-energy dispersive X-ray spectroscopy(FESEM-EDX),thermal gravimetry/differential thermal analysis(TG/DTA),and the four-point probe technique(4PPT).XRD analysis reveals that the samples Bi_(1-x-y)Gd_(x)Dy_(y)O_(1.5)(y=0.05/x=0.05,0.10,0,15,and 0.20,and x=0.05/y=0.10,0.15,and 0.20) exhibit a stable face-centered cubic δ-phase and a mixed-phase crystallographic structure.The XRD analysis of the stabilized δ-phase suggests that the prepared oxides show a face-centered cubic(FCC) structure with a space group of Fm-3m.FESEM micrographs reveal that the composition Bi_(0.90)Gd_(0.05)Dy_(0.05)O_(1.5) has no significant holes.Nevertheless,an evident increase in the pore formation is observed as the amount of Gd_(2)O_(3) increases until it reaches 20%.This finding suggests that dense pellets are formed during the sintering process at 900-1000℃.The DTA analyses were performed to verify the phase stability,which agrees with the XRD results.The electrochemical performance of the synthesized Dy-Gd co-doped Bi_(2)O_(3)solid electrolyte system was evaluated and analyzed in detail by using the electrochemical impedance spectroscopy(EIS) technique,Based on EIS and conductivity measurements,Bi_(0.75)Gd_(0.20)Dy_(0.05)O_(1.5) exhibits the lowest activation energy of 0.519 eV and the highest conductivity value of 0.398 S/cm at 627℃compared to the other samples;this composition can be used as a solid electrolyte for intermediatetemperature solid oxide fuel cells(SOFCs).

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.

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.

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.

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.

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.

Status and prospects of intermediate temperature solid oxide fuel cells

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.

A dynamic infiltration technique to synthesize nanolayered cathodes for high performance and robust solid oxide fuel cells

Solution infiltration is a popular technique for the surface modification of solid oxide fuel cell(SOFC)cathodes.However,the synthesis of nanostructured SOFC cathodes by infiltration is a tedious process that often requires several infiltration and high temperature(≥500℃)calcination cycles.Moreover,fabricating large-area nanostructured cathodes via infiltration still requires serious attention.Here,we propose a facile and scalable urea assisted ultrasonic spray infiltration technique for nanofabrication of SOFC cathodes.It is demonstrated that by using urea as a precipitating agent,the calcination after each infiltration cycle can be omitted and the next infiltration can be performed just after a drying step(≤100℃).Finally,the precipitates can be converted into a desired catalyst phase in single calcination thus,a nanostructured cathode can be fabricated in a much faster manner.It is also shown that the low calcination temperature of the cathode(≤900℃)can produce highly durable SOFC performance even without employing a Ce_(0.9)Gd_(0.1)O_(2)(GDC)diffusion barrier layer which provides the ease of SOFC fabrication.While coupling with an ultrasonic spray technique,the urea assisted infiltration can be scaled up for any desired cathode area.La_(0.6)Sr_(0.4)Co_(0.2)Fe_(0.8)O_(3) nanolayered cathode was fabricated and it was characterized by scanning electron microscope(SEM),X-ray diffraction(XRD),and transmission electron microscopy(TEM)techniques.SEM showed the formation of a nanolayer cathode just after 5 cycles of the urea assisted infiltration while the XRD and TEM confirmed the phase and stoichiometric uniformity of the 100 nm cathode nanolayer.The effectiveness of the newly developed technique was further verified by the stable operation of a GDC buffer layer free SOFC having an active cathode area of 25 cm^(2) during a 1200 h durability test.The research outcomes propose urea assisted ultrasonic spray infiltration as a facile,scalable,and commercially viable method for the fabrication of durable nanostructured SOFC cathodes.

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.

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, 17500mA·cm-2 and 200mW·cm-2, are obtained with pure H2S flow rate of 50ml·min-1 and air flow rate of 100ml·min-1 at 850℃.

The Effect of Fabrication Conditions for GDC Buffer Layer on Electrochemical Performance of Solid Oxide Fuel Cells

A Gd-doped ceria（GDC） buffer layer is required between a conventional yttria-stabilized zirconia（YSZ） electrolyte and a La-Sr-Co-Fe-O3（LSCF） cathode to prevent their chemical reaction. In this study,the effect of varying the conditions for fabricating the GDC buffer layer, such as sintering temperature and amount of sintering aid, on the solid oxide fuel cell（SOFC） performance was investigated. A finer GDC powder（i.e., ultra-high surface area）, a higher sintering temperature（1290℃）, and a larger amount of sintering aid（12%） resulted in improved densification of the buffer layer; however, the electrochemical performance of an anode-supported cell containing this GDC buffer layer was poor. These conflicting results are attributed to the formation of（Zr, Ce）O2 and/or excess cobalt grain boundaries（GBs） at higher sintering temperatures with a large amount of sintering aid（i.e., cobalt oxide）. A cell comprising of a cobalt-free GDC buffer layer, which was fabricated using a low-temperature process, had lower cell resistance and higher stability. The results indicate that electrochemical performance and stability of SOFCs strongly depend on fabrication conditions for the GDC buffer layer.