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.

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.

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.

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.

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.

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.

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.

Ni doped La_(0.6)Sr_(0.4)FeO_(3-δ) symmetrical electrode for solid oxide fuel cells

The conventional Ni cermet anode suffers from severe carbon deposition and sulfur poisoning when fossil fuels are used. Alternative anode materials are desired for high performance hydrocarbon fuel solid oxide fuel cells （SOFCs）. We report the rational design of a very active Ni doped La0.6Sr0.4FeO3‐δ（LSFN） electrode for hydrocarbon fuel SOFCs. Homogeneously dispersed Ni‐Fe alloy nanoparticles were in situ extruded onto the surface of the LSFN particles during the operation of the cell. Sym‐metric SOFC single cells were prepared by impregnating a LSFN precursor solution onto a YSZ （yt‐tria stabilized zirconia） monolithic cell with a subsequent heat treatment. The open circuit voltage of the LSFN symmetric cell reached 1.18 and 1.0 V in humidified C3H8 and CH4 at 750？？, respective‐ly. The peak power densities of the cells were 400 and 230 mW/cm2 in humidified C3H8 and CH4, respectively. The electrode showed good stability in long term testing, which revealed LSFN has good catalytic activity for hydrocarbon fuel oxidation.

Samaria-doped Ceria Modified Ni/YSZ Anode for Direct Methane Fuel in Tubular Solid Oxide Fuel Cells by Impregnation Method

A porous NiO/yttria-stabilized zirconia was prepared by gel casting technique. anode substrate for tubular solid oxide fuel cells Nano-scale samaria-doped ceria （SDC） particles were formed onto the anode substrate to modify the anode microstructure by the impregnation of solution of Sm（NO3）3 and Ce（NO3）3. Electrochemical impedance spectroscopy, current-voltage and current-powder curves of the cells were measured using an electrochemical workstation. Scanning electron microcopy was used to observe the microstructure. The results indicate that the stability of the performance of the cell operated on humidified methane can be significantly improved by incorporating the nano-structured SDC particles, compared with the unmodified cell. This verifies that the coated SDC electrodes are very effective in suppressing catalytic carbon formation by blocking methane from approaching the Ni, which is catalytically active towards methane pyrolysis. In addition, it was found that a small amount of deposited carbon is beneficial to the performance of the anode. The cell showed a peak power density of 225 mW/cm^2 when it was fed with H2 fuel at 700 ℃, but the power density increased to 400 mW/cm^2 when the fuel was switched from hydrogen to methane at the same flow rate. Methane conversion achieved about 90%, measured by gas chromatogram with a 10.0 mL/min flow rate of fuel at 700 ℃. Although the carbon deposition was not suppressed absolutely, some deposited carbon was beneficial for performance improvement.

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.

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.

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.

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.

Electrochemical performance and stability of Sr-doped LaMnO_(3)-infiltrated yttria stabilized zirconia oxygen electrode for reversible solid oxide fuel cells

Porous Sr-doped lanthanum manganite–yttria stabilized zirconia(LSM–YSZ)oxygen electrode is prepared by an infiltration process for a reversible solid oxide fuel cell(RSOFC).X-ray diffraction and SEM analysis display that perovskite phase LSM submicro particles are evenly distributed in the porous YSZ matrix.Polarization curves and electrochemical impedance spectra are conducted for the RSOFC at 800 and 850C under both SOFC and SOEC modes.At 850℃,the single cell has the maximum power density of~726 mW/cm^(2)under SOFC mode,and electrolysis voltage of 1.35 V at 1 A/cm^(2)under SOEC mode.Fuel cell/water electrolysis cycle shows the cell has good performance stability during 6 cycles,which exhibits the LSM–YSZ oxygen electrode has high electrochemical performance and good stability.The results suggest that netw ork-like LSM–YSZ electrode made by infiltration process could be a promising oxygen electrode for high temperature RSOFCs.