Synthesis and characterization of La0.75Sr0.25Cr0.9M0.1O3 perovskites as anodes for CO-fuelled solid oxide fuel cells

A series of La_0.75Sr_0.25Cr_0.9M_0.1O₃ (M = Mn, Fe, Co, Ni) perovskite compounds was synthesized by a modified citrate sol-gel route and employed as anode electrodes on YSZ electrolyte supported SOFC cells. Materials and anode electrodes were characterized for their chemical composition, crystal structure and film morphology. The electrochemical performance of the prepared anodes was evaluated in button cells under SOFC operation with CO/CO₂ mixtures in the temperature range of 900–1000 °C. It was shown that the performance of the perovskite materials in terms of maximum power density follows the sequence Fe > Ni > Co > Mn, based on the substitution cation into the B-site. No carbon deposition was observed under the operating conditions examined, even for prolonged (120 h) exposure to the reaction mixture.     

Operational Inhomogeneities in La0.9Sr0.1Ga0.8Mg0.2O3–δ Electrolytes and La0.8Sr0.2Cr0.82Ru0.18O3–δ–Ce0.9Gd0.1O2–δ Composite Anodes for Solid Oxide Fuel Cells

The electrolyte/anode interface in solid oxide fuel cells with La_0.9Sr_0.1Ga_0.8Mg_0.2O_3–δ electrolytes and composite anodes containing La_0.8Sr_0.2Cr_0.82Ru_0.18O_3–δ and Ce_0.9Gd_0.1O_2–δ (GDC) was studied using transmission electron microscope Z‐contrast imaging and energy dispersive X‐ray spectroscopy. The anode/electrolyte interface of an operated cell had numerous defective regions in the electrolyte, immediately adjacent to anode GDC particles. These areas had a different chemical composition than other electrolyte regions and were crystallographically inhomogeneous. These regions were not observed in a cell reduced in hydrogen that was not operated, suggesting that they were the result of combined electrical and chemical potential gradients present during cell operation. Ru nanoparticles were observed on the chromite surfaces of the operated.     

La1.7Ca0.3Ni0.75Cu0.25O4‐δ‐Layered Perovskite as Cathode on La0.9Sr0.1Ga0.8Mg0.2O3 or Ce0.8Gd0.2O2 Electrolyte for Intermediate Temperature Solid Oxide Fuel Cells

La₂NiO_4+δ‐based oxides, mixed ionic–electronic conductors with K₂NiF₄‐type structure, have been considerably investigated in recent decades as electrode materials for advanced solid oxide fuel cells (SOFCs) due to their high electrical conductivity and oxidation reduction reaction (ORR) activity. In this study, La_1.7Ca_0.3Ni_0.75Cu_0.25O_4+δ was investigated as a potential cathode on La_0.9Sr_0.1Ga_0.8Mg_0.2O₃ electrolyte support. Furthermore, La_1.7Ca_0.3Ni_0.75Cu_0.25O_4+δ was examined on thin Ce_0.8Gd_0.2O₂ (GDC) electrolyte with Ni‐GDC anode support for intermediate temperature SOFCs (IT‐SOFCs). La_1.7Ca_0.3Ni_0.75Cu_0.25O_4‐δ cathode with gadolinium doped ceria (GDC) electrolyte and NiO‐GDC anode support showed a maximum power density of 0.75 W/cm² in H₂ and lower polarization resistance, Rp (<0.1 Ω cm²), in impedance spectroscopy at 700°C.     

Effects of mass fraction of La0.9Sr0.1Cr0.5Mn0.5O3-δ and Gd0.1Ce0.9O2-δ composite anodes for nickel free solid oxide fuel cells

The optimal anode mass fraction of La_0.9Sr_0.1Cr_0.5Mn_0.5O_3-δ (LSCM) and Gd_0.1Ce_0.9O_2-δ (GDC) is evaluated in this study. The anodes with GDC share of 30–100 wt.% are investigated. Initial polarization resistance decreased as the GDC share increased. However, anodes with GDC share over 80 wt.% significantly deteriorated in the degradation tests. Nano-scale cracks were observed in the GDC phase at the grain boundaries after the test. These nano-cracks were not observed in composite anodes, from which it is implied that LSCM has stabilization effect on GDC structure. The mass fraction of LSCM : GDC = 30 : 70 wt.% is found to be optimal in terms of initial electrochemical performance and stability. The optimal LSCM-GDC shows lower polarization resistance than conventional Ni-YSZ at low temperatures, which is comparable to Ni-GDC anode.     

Proton diffusivity in the BaZr<Subscript>0.9</Subscript>Y<Subscript>0.1</Subscript>O<Subscript>3−δ</Subscript> proton conductor

The thermally activated proton diffusion in BaZr_0.9Y_0.1O_3−δ was studied with electrochemical impedance spectroscopy (IS) and quasi-elastic neutron scattering (QENS) in the temperature range 300–900 K. The diffusivities for the bulk material and the grain boundaries as obtained by IS obey an Arrhenius law with activation energies of 0.46 eV and 1.21 eV, respectively. The activation energies obtained by IS for the bulk are 0.26 eV above 700 K and 0.46 eV, below 700 K. The total diffusivity as obtained by IS is by one order of magnitude lower than the microscopic diffusivity as obtained by QENS. The activation energies obtained by QENS are 0.13 eV above 700 K and 0.04 eV, below 700 K. At about 700 K, the diffusion constants for IS and QENS have a remarkable crossover, suggesting two processes with different activation energies.     

Microstructure and electrical conductivity of La0.9Sr0.1 Ga0.8Mg0.2O2.85-Ce0.8Gd0.2O1.9 composite electrolytes for SOFCs

(100-x) wt.% La_0.9Sr_0.1 Ga_0.8Mg_0.2O_2.85 - x wt.% Ce_0.8Gd_0.2O_1.9 (x = 0, 5, 10, 20) electrolytes were prepared by solid-state reaction. The composition, microstructure, and electrical conductivity of the samples were investigated. At 300 ~ 600°C, the pure La_0.9Sr_0.1 Ga_0.8Mg_0.2O_2.85 electrolyte has a higher conductivity compared to the composite electrolytes, but at 650 ~ 800°C the 95 wt.% La_0.9Sr_0.1 Ga_0.8Mg_0.2O_2.85 - 5 wt.% Ce_0.8Gd_0.2O_1.9 composite electrolyte presents the highest conductivity, reaching 0.035 S cm⁻¹ at 800°C. The cell performances based on La_0.9Sr_0.1 Ga_0.8Mg_0.2O_2.85-Ce_0.8Gd_0.2O_1.9 electrolytes were measured using Sr₂CoMoO₆-La_0.9Sr_0.1 Ga_0.8Mg_0.2O_2.85 as anode and Sr₂Co_0.9Mn_0.1NbO₆ -La_0.9Sr_0.1 Ga_0.8Mg_0.2O_2.85 as cathode, respectively. At 800°C, the measured open-circuit voltages are higher than 1.08 V, and the maximum power density and current density of the fuel cell prepared with 95 wt.% La_0.9Sr_0.1 Ga_0.8Mg_0.2O_2.85 - 5 wt.% Ce_0.8Gd_0.2O_1.9 electrolyte reach 192 mW cm⁻² and 720 mA cm⁻², respectively.     

Investigation of the conditions for synthesis of Ce<Subscript>0.9</Subscript>Y<Subscript>0.1</Subscript>O<Subscript>2</Subscript> dense coatings

The conditions for preparation of Ce_0.9Y_0.1O₂ (CYO) oxide coatings on La_0.8Sr_0.2MnO₃ (LSM) ceramic substrates by screen printing were investigated. The CYO compound was synthesized by the pyrolysis of polymer-salt composites with the aim of producing submicron powders with a uniform size distribution. Transmission electron microscopy of the microstructure of the CYO compound synthesized with ethylene glycol revealed that the synthesis product consists of ultrafine crystalline particles with an average size of 5–15 nm. The use of CYO nanopowders made it possible to prepare rather dense single-layer coatings on LSM substrates. It was demonstrated that annealing of the coatings at high temperatures leads to the recrystallization and coarsening of particles.     

La0.5Sr0.5Fe0.9Mo0.1O3-δ-CeO2 anode catalyst for Co-Producing electricity and ethylene from ethane in proton-conducting solid oxide fuel cells

A La_0.5Sr_0.5Fe_0.9Mo_0.1O_3-δ-CeO₂ (LSFM-CeO₂) composite was prepared by impregnating CeO₂ into porous La_0.5Sr_0.5Fe_0.9Mo_0.1O_3-δ perovskite and was used as an anode material for proton-conducting solid oxide fuel cells (SOFCs). The maximum power densities of the BaZr_0.1Ce_0.7Y_0.2O_3-δ (BZCY) electrolyte-supported single cell with LSFM-CeO₂ as the anode reached 291 mW cm^?2 and 190 mW cm^?2 in hydrogen and ethane fuel at 750 °C, respectively, which are significantly higher than those of a single cell with only LSFM as the anode. Additionally, the ethylene selectivity and ethylene yield from ethane for the fuel cell at 750 °C were as high as 93.4% and 37.1%, respectively. The single cell also showed negligible degradation in performance and no carbon deposition during continuous operation for 22 h under an ethane fuel atmosphere. The improved electrochemical performance due to the impregnation of CeO₂ can be a result of enhanced electronic and ionic conductivity, abundant active sites, and a broad three-phase interface in the resultant composite anode. The LSFM-CeO₂ composite is believed to be a promising anode material for proton-conducting SOFCs for co-producing electricity and high-value chemicals from hydrocarbon fuels.     

Electric field-assisted sintering anode-supported single solid oxide fuel cell

Cosintering (La_0.84Sr_0.16MnO₃ thin-film cathode/ZrO₂: 8 mol% Y₂O₃ thin-film solid electrolyte/55 vol.% ZrO₂:8 mol% Y₂O₃ + 45 vol.% NiO anode, ϕ = 12 × 1.5 mm thick pellet) was achieved by applying an electric field for 5 min at 1200°C. Impedance spectroscopy measurements of the anode-supported three-layer cell show an improvement of the electrical conductivity in comparison to that of a conventionally sintered cell. The scanning electron microscopy images of the cross-sections of electric field-assisted pressureless sintered cells show a fairly dense electrolyte and porous anode and cathode. Joule heating, resulting from the electric current due to the application of the AC electric field, is suggested as responsible for sintering. Dilatometric shrinkage curves, electric voltage and current profiles, impedance spectroscopy diagrams, and scanning electron microscopy micrographs show how anode-electrolyte-cathode ceramic cells can be cosintered at temperatures lower than the usually required.     

Direct electrochemical reduction of Dy<Subscript>2</Subscript>O<Subscript>3</Subscript> in CaCl<Subscript>2</Subscript> melt

The electrochemical reduction of Dy₂O₃ in CaCl₂ melt was studied. The cyclic voltammetry, chronoamperometry, AC impedance and constant voltage electrolysis were employed. A single cathodic current peak in the cyclic voltammogram and one response semicircle in the AC impedance spectrum were observed, supporting a one-step electrochemical reduction mechanism of Dy₂O₃. No intermediates were observed by XRD, which confirmed the following electrochemical reduction sequence: Dy₂O₃ → Dy. The charge transfer resistances and the activation energies involved in the electrochemical reduction step of Dy₂O₃ were obtained by simulating the AC impedance spectra with equivalent circuits. The electrochemical reduction reaction of Dy₂O₃ is controlled by the charge transfer process at a low voltage range and by the diffusion process at a high voltage range.     

Synthesis and electrochemical characterization of La0.75Sr0.25Mn0.5Cr0.5−xAlxO3, for IT- and HT-SOFCs

The main emphasis of this work is to create a new perovskite material with three different compositions (La_0.75Sr_0.25Mn_0.5Cr_0.5−xAlxO₃, x = 0.1, 0.2, 0.3) applied in both Intermediate- and High-temperature Solid Oxide Fuel Cells (IT- and HT-SOFCs). Perovskite-type polycrystalline La_0.75Sr_0.25Mn_0.5Cr_0.5−xAl_xO_3−δ (x = 0.1, 0.2, 0.3) powders were synthesized and formed in a single phase structure by a dry chemistry route (standard solid-state reaction method). The effect of Al doping on physicochemical and surface properties has been discovered. The compounds were crystallized in single phase rhombohedral symmetry (R-3C Space. Group). Total conductivity of Al doping in wet 5% H₂ was higher than both dry 5% H₂ and air. The obtained results enhance the electro-catalytic performance and the material conductivity as well, which will be good for anode materials in IT- and HT-SOFCs and the optimum doping is 10%.     

Development of MnO<Subscript>2</Subscript>-incorporated high performance aluminum alloy matrix sacrificial anodes

Manganese dioxide, a potential catalyst in many electrochemical reactions, was explored as an effective activator in Al + 5% Zn alloy sacrificial anodes. The catalytic influence of MnO₂ on the anodes was micro-structurally and electrochemically characterized using different electrochemical techniques. The process of incorporation of MnO₂ not only improved the grain size but also the galvanic performance of the anodes significantly. A galvanic performance as high as 80% was achieved by incorporating an optimum quantity (0.5%) of MnO₂ in the anode matrix. High and steady active open circuit potential, very low polarization and substantial reduction in self corrosion were achieved during galvanic exposure tests. Effective activation of the anodes by MnO₂ was also revealed by the results of electrochemical impedance analysis. The tolerance to biofouling on the anode surface was studied by quantifying the number of micro-organisms on the anode surface after immersing in natural sea water containing the micro-organisms.     

Electrochemical characterization of La<Subscript>0.8</Subscript>Sr<Subscript>0.2</Subscript>MnO<Subscript>3</Subscript>-coated NiO as cathodes for molten carbonate fuel cells

La_0.8Sr_0.2MnO₃ was coated on porous NiO cathode using a simple combustion process. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were employed in the cathode characterizations. The electrochemical behavior of La_0.8Sr_0.2MnO₃-coated NiO cathodes (LSM–NiO) were also evaluated in a molten 62 mol%Li₂CO₃+38 mol%K₂CO₃ eutectic at 650 °C under the standard cathode gas condition by electrochemical impedance spectroscopy (EIS). The impedance response of the NiO and LSM–NiO cathode at different immersion times is characterized by the presence of depressed semicircles in the high frequency range and an extension at low frequencies. Impedance analysis showed that the behavior of the developed cathode was similar to that of the conventional nickel oxide cathode. The LSM–NiO showed a lower dissolution and a better catalytic efficiency superior to the state-of-the-art NiO value. Thus the cathode prepared with coating method to coat La_0.8Sr_0.2MnO₃ on the surface of NiO cathode is able to reduce the solubility of NiO to lengthen the lifetime of MCFC while maintaining the advantages of NiO cathode. The LSM–NiO shows promise as an alternate cathode in molten carbonate fuel cells (MCFCs).     

Effects of La<Subscript>2</Subscript>O<Subscript>3</Subscript> on ZrO<Subscript>2</Subscript> supported Ni catalysts for autothermal reforming of CH<Subscript>4</Subscript>

The effect of La₂O₃ content in Ni-La-Zr catalyst was investigated for the autothermal reforming (ATR) of CH₄. The catalysts were prepared by the coprecipitation method and had a mesoporous structure. Temperature programmed reduction (TPR) and X-ray photoelectron spectroscopy (XPS) indicated that a strong interaction developed between Ni species and the support with the addition of La₂O₃. Thermogravimetric analysis (TGA) and H₂-pulse chemisorption showed that the addition of La₂O₃ led to well dispersed NiO molecules on the support. Ni-La-Zr catalysts gave much higher CH₄ conversion than Ni-Zr catalyst. The Ni-La-Zr containing 3.2 wt% La₂O₃ showed the highest activity. The optimum conditions for maximal CH₄ conversion and H₂ yield were H₂O/CH₄=1.00, O₂/CH₄=0.75. Under these conditions, CH₄ conversion of 83% was achieved at 700 °C. In excess O₂ (O₂/CH₄>0.88), the catalytic activity was decreased due to sintering of the catalyst.     

Green synthesis and characterisation of nanocrystalline NiO-GDC powders with low activation energy for solid oxide fuel cells

This work reports the preparation of nanocrystalline Ni-Gd_0.1Ce_0.9O_1.95 (NiO-GDC) anode powders using a novel single-step co-precipitation synthesis method (carboxylate route) based on ammonium tartrate as a low-cost green precipitant. The thermogravimetric analysis (TGA) of the synthesised powder showed the complete calcination/crystallisation of the resultant precipitates to take place at 500 °C. The prepared NiO-GDC powder was coated on a GDC electrolyte disc and co-sintered at 1300 °C. A mixture of La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ and GDC was used as the cathode material and subsequently coated onto the anode-electrolyte bilayer, resulting in the fabrication of a NiO-GDC|GDC|La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ-GDC cell. The crystallite size of both NiO and CeO₂ phases were estimated using the X-ray powder diffraction (XRD) profiles and were calculated to be ~14 nm. Applied H₂ temperature-programmed reduction (H₂-TPR) analysis indicated a synergetic effect among different anode composites' constituents, where an intense interaction between the dispersed NiO nanocrystalline particles and the GDC crystallite phase had weakened the metal-oxygen bonds in the synthesised anode composites, resulting in a strikingly high catalytic activity at temperatures as low as 300 °C. The electrochemical impedance spectroscopy (EIS) and the electrochemical performance of the fabricated cells were measured over a broad range of operating temperatures (500–750 °C) and H₂/Ar-ratios of the anode fuel (e.g. 100%–15%). Quantitative analysis from the EIS data and the application of the distribution of relaxation times (DRT) method allowed for the estimation of the activation energies of the anodic high and intermediate frequency processes that were 0.45 eV and 0.76 eV, respectively. This is the first report of a NiO-GDC synthesis, where a considerable improvement in activation energy is observed at the low-temperature region. Such low activation energies were later associated with the adsorption/desorption process of water molecules at the surface of NiO-GDC composite, indicating a high activity towards hydrogen oxidation.     

Ni/La<Subscript>2</Subscript>O<Subscript>3</Subscript>-ZrO<Subscript>2</Subscript> catalyst for hydrogen production from steam reforming of acetic acid as a model compound of bio-oil

Hydrogen production from steam reforming of acetic acid was investigated over Ni/La₂O₃-ZrO₂ catalyst. A series of Ni/La₂O₃-ZrO₂ catalysts were synthesized by sol-gel method coupled with wet impregnation, which was characterized by XRD, BET, TEM, EDS, TG, SEM and TPR. Catalytic activity of Ni/La₂O₃-ZrO₂ was evaluated by steam reforming of acetic acid at the temperature range of 550-750 °C. The tetragonal phase La_0.1Zr_0.9O_1.95 is formed through the doping of La₂O₃ into the ZrO₂ lattice and nickel species are highly dispersed on the support with high specific surface area. H₂ yield and CO₂ yield of Ni/La₂O₃-ZrO₂ catalyst with 15%wt Ni reaches 89.27% and 80.41% at 600 °C, respectively, which is attributed to high BET surface area and sufficient Ni active sites in strong interaction with the support. 15%wt Ni supported on La₂O₃-ZrO₂ catalyst maintains relatively stable catalytic activities for a period of 20 h.     

Fabrication of Solid Oxide Fuel Cells with a Thin (La0.9Sr0.1)0.98(Ga0.8Mg0.2)O3–δ Electrolyte on a Sr0.8La0.2TiO3 Support

This paper describes Sr_0.8La_0.2TiO₃ (SLT)‐supported solid oxide fuel cells with a thin (La_0.9Sr_0.1)_0.98Ga_0.8Mg_0.2O_3–δ (LSGM) electrolyte and porous LSGM anode functional layer (AFL). Optimized processing for the SLT support bisque firing, LSGM electrolyte layer co‐firing, and LSGM AFL colloidal composition is presented. Cells without a functional layer yielded a power density of 228 mW cm^–2 at 650 °C, while cells with a porous LSGM functional layer yielded a power density of 434 mW cm^–2 at 650 °C. Cells with an AFL yielded a higher open circuit voltage, possibly due to reduced Ti diffusion into the electrolyte. Infiltration produced Ni nanoparticles within the support and AFL, which proved crucial for the electrochemical activity of the anode. Power densities increased with increasing Ni loadings, reaching 514 mW cm^–2 at 650 °C for 5.1 vol.% Ni loading. Electrochemical impedance spectroscopy analysis indicated that the cell resistance was dominated by the cathode and electrolyte resistance with the anode resistance being relatively small.     

Nanofiber-based LaxSr1−xTiO3-GdyCe1−yO2−δ composite anode for solid oxide fuel cells

La_xSr_1−xTiO₃ (LST) nanofibers with pure perovskite structure, smooth surface, uniform diameter and length are prepared by electrospinning technique, and applied as scaffolds of La_xSr_1−xTiO₃-Gd_yCe_1−yO_2−δ (LST-GDC) composite anodes for SOFCs. The optimal La doping ratio of LST scaffold has been found to be 0.4, and 0.2 the optimal Gd doping ratio of GDC impregnation phase. The LST:GDC optimal mass ratio of nanofiber-based composite anode has been found to be 1:1.5481, and the composite anode (electrolyte is yttria-stabilized zirconia) to show low interfacial polarization resistances of 0.7309, 0.4688 and 0.2966 Ω cm² at 800, 850 and 900 °C, respectively. In addition, the microstructure of LST materials has been found to plays an important role on the electrochemical performance of the anodes, and the LST nanofiber scaffolds to show the higher porosity leading to a larger triple phase (ionic conduction phase, electronic conduction phase and gas phase) boundary (TPB) area for the composite anodes.     

Oxygen permeability and structural stability of La<Subscript>0.6</Subscript>Sr<Subscript>0.4</Subscript>Co<Subscript>0.2</Subscript>Fe<Subscript>0.8</Subscript>O<Subscript>3−<Emphasis Type="Italic">δ</Emphasis></Subscript> membrane

La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ oxides were synthesized by citrate method and hydrothermal method. The oxides prepared by citrate method are perovskite type structure, while the oxides by hydrothermal method have a small amount of secondary phase in the powder. Pyrex glass seal and Ag melting seal provided reliable gas-tight sealing of disk type dense membrane in the range of operation temperature, but commercial ceramic binder could not be removed from the support tube without damage to the tube or membrane. Though the degree of gas tightness increases in the order of glass>Ag>ceramic binder, in the case of glass seal, the undesired spreading of glass leads to an interfacial reaction between it and the membrane and reduction of effective permeation area. The oxygen flux of La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ membrane increases with increasing temperature and decreasing thickness, and the oxygen permeation flux through 1.0 mm membrane exposed to flowing air (P _h =0.21 atm) and helium (P₁=0.037 atm) is ca. 0.33 ml/cm²·min at 950 °C. X-ray diffraction analysis for the membrane after permeation test over 160 h revealed that La₂O₃ and unknown compound were formed on the surface of membrane. The segregation compounds of surface elements formed on both surfaces of membrane irrespective of spreading of glass sealing material. This paper was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

Novel Metal Substrates for High Power Metal‐supported Solid Oxide Fuel Cells

Novel high permeable porous Ni‐Mo substrates with different area densities of straight gas flow channels are successfully developed to improve the hydrogen fuel gas and the water byproduct diffusion in the anode and supporting substrate. Metal‐supported cell A, cell B and cell C with 5 × 5 cm² supporting substrates are fabricated by atmospheric plasma spraying processes, these cells have the material structure of Ni‐Mo/LSCM (La_0.75Sr_0.25Cr_0.5‐Mn_0.5O_3–δ)/NiO‐LDC(Ce_0.55La_0.45O_2–δ)/SDC(Sm_0.15Ce_0.85O_3–δ)/LSGM (La_0.8Sr_0.2Ga_0.8Mg_0.2O_3–δ)/SSC(Sm_0.5Sr_0.5CoO_3–δ). Cell A is supported by a conventional porous Ni‐Mo substrate without straight gas flow channels, cell B and cell C are supported respectively by the novel high permeable porous Ni‐Mo substrates with 1.5 and 2.73 channels per square centimeter. The power densities at 0.8 V and 750 °C are 550, 998 and 1,161 mW cm⁻² for cell A, cell B and cell C respectively. The 100 h durability test at the constant current density of 400 mA cm⁻² and 650 °C shows cell B and cell C have smaller degradation rates than cell A. The results obtained from AC impedance and circuit model analyses indicate that the electrolyte ohm and the cathode polarization resistances are significantly reduced by introducing straight gas flow channels into the supporting substrate.