Electrical conductivity of textured Sm and Nd Co-doped CeO2 thin-film electrolyte

Nanocrystalline thin-film electrolytes of Sm³⁺ and Nd³⁺ co-doped ceria have been deposited on polycrystalline alumina substrates via RF magnetron sputtering. It is found that with the increase of substrate temperature from room temperature to 600 °C, the structure of the film varies from (1 1 1) preferred orientation to random orientation, accompanied by an enhancement in electrical conductivity. It is estimated that the activation energy for oxygen ion migration along (1 1 1) orientation may be higher than other crystal orientations, resulting in a lower conductivity of the (1 1 1) barrier textured co-doped ceria film electrolyte. It also indicates that the electrical conduction is predominantly due to the oxygen ions.     

Fabrication of Sm and Nd co-doped CeO2 thin-film electrolytes by radio frequency magnetron sputtering

Nanocrystalline Sm³⁺ and Nd³⁺ co-doped CeO₂ thin-film electrolytes with high in-plane electric conductivities have been deposited via radio frequency magnetron sputtering. The results show that with increased RF power or decreased pressure, a reduction in the level of porosity of the film takes place, along with an increased electric conductivity. Maximum electric conductivity of 9 × 10⁻³ S cm⁻¹ at 500 °C was achieved with optimal sputtering process. It also indicates that with the change of the substrate from single crystal alumina to polycrystalline alumina, the film structure varies from (1 1 1) preferred orientation to random orientation, accompanied by an enhancement in electric conductivity. Compared with alumina substrates, the quartz substrate shows a negative effect on electric conductivity.     

Synthesis and sintering behavior of La0.8Sr0.2CrO3 by a glycine nitrate process

La_0.8Sr_0.2CrO₃ powder was synthesized by a glycine nitrate process from an aqueous solution of lanthanum, strontium, and chromium nitrates, and glycine. The apparent density, size and morphology of the La_0.8Sr_0.2CrO₃ powder depended on the glycine-to-nitrate ratio. However, the pH value of the precursor solution had no significant effect on these properties. It was found that a single-phase perovskite, La_0.8Sr_0.2CrO₃, was synthesized when the dried ash was calcined at 1200 °C for 5 h. A secondary minor phase, SrCrO₄, was observed in the powder calcined at temperatures lower than 1100 °C. The presence of the SrCrO₄ phase has a significant effect on the sinterability and microstructural evolution of the La_0.8Sr_0.2CrO₃. A relative density higher than 90% could be achieved when the 1000 °C-calcined La_0.8Sr_0.2CrO₃ powder was sintered at 1450 °C.     

Samarium doped ceria (SDC) synthesized by a metal triethanolamine complex decomposition method: Characterization and an ionic conductivity study

Samarium doped ceria (SDC) powders as solid electrolyte ceramics were successfully prepared via thermal decomposition of metal organic complexes containing triethanolamine (TEA) as a ligand. The SDC powders synthesized using various samarium doping contents were characterized by X-ray diffractometry, scanning electron microscopy, X-ray absorption spectroscopy, energy dispersive X-ray spectroscopy and Brunauer-Emmett-Teller (BET) analysis. The influences of samarium doping and the calcination temperature on the characteristics of the SDC materials were thoroughly investigated. An appropriate temperature for SDC powder calcination was identified by thermogravimetric analysis to be 600 °C. After sintering the calcined SDC powders at 1500 °C to obtain highly dense ceramic pellets, the electrical conductivity of the materials was examined by impedance spectroscopy. The influence of percentage of Sm³⁺ dopants in SDC materials on the observed conductivity were explained by correlating with the detailed analysis of the local structure and environment of Sm³⁺ within the SDC materials by using X-ray absorption spectroscopy. The conductivities of the SDC products reported in this work indicate that they are promising candidates for solid electrolytes in solid oxide fuel cell applications.     

Combustion synthesis and characterization of Cu-Sm co-doped CeO2 electrolytes

Nano-sized CSO (Ce_0.80Sm_0.20O_2−δ) and CSCO (Ce_0.79Sm_0.20Cu_0.01O_2−δ) were synthesized by the PVA assisted combustion method, and then characterized by the structure of PVA-cation complexes and nano-powders, as well as mechanical and electrical performance after sintering. The results indicate that the PVA-cation complexes (PVA-(Ce³⁺,Sm³⁺) and PVA-(Ce³⁺,Sm³⁺,Cu²⁺)) were formed by coordinating metal cations to hydroxyl groups, as well as the COO⁻¹ group derived from the oxidation of PVA with NO₃⁻¹. Low temperatures (around 200 °C) caused intense combustion reactions, resulting in the direct crystallization of cubic fluorite nano-CSO (10-20 nm) and nano-CSCO (10-15 nm) crystals with homogeneous element distribution. This slight compositional modification of CSO by co-doping with 1 mol% CuO resulted in a significantly lowered densification temperature, as well as enhanced mechanical and electrical property. The strength improvement can be ascribed to the dense and fine-grained microstructure without normal grain coarsening, resulting in a transgranular-dominant fracture mode during strength testing.     

Nano-sized Sm0.5Sr0.5CoO3−δ as the cathode for solid oxide fuel cells with proton-conducting electrolytes of BaCe0.8Sm0.2O2.9

Nano-sized Sm_0.5Sr_0.5CoO_3−δ (SSC) was fabricated onto the inner face of porous BaCe_0.8Sm_0.2O_2.9 (BCS) backbone by ion impregnation technique to form a composite cathode for solid oxide fuel cells (SOFCs) with BCS, a proton conductor, as electrolyte. The electro-performance of the composite cathodes was investigated as function of fabricating conditions, and the lowest polarization resistance, about 0.21 Ω cm² at 600 °C, was achieved with BCS backbone sintered at 1100 °C, SSC layer fired at 800 °C, and SSC loading of 55 wt.%. Impedance spectra of the composite cathodes consisted of two depressed arcs with peak frequency of 1 kHz and 30 Hz, respectively, which might correspond to the migration of proton and the dissociative adsorption and diffusion of oxygen, respectively. There was an additional arc peaking at 1 Hz in the Nyquist plots of a single cell, which should correspond to the anode reactions. With electrolyte about 70 μm in thickness, the simulated anode, cathode and bulk resistances of cells were 0.021, 0.055 and 0.68 Ω cm² at 700 °C, relatively, and the maximum power density was 307 mW cm⁻² at 700 °C.     

Assessment of structurally stable cubic Bi12TiO20 as intermediate temperature solid oxide fuels electrolyte

Colloid processing and subsequent pressure filtration were used to prepare 14.3 mol% TiO₂ doped Bi₂O₃ (Bi₁₂TiO₂₀, 14BTO) as solid oxide fuel cell electrolyte. Materials characterization and electrical behaviors of 14BTO samples were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and two-point probe DC conductivity. A pure 14BTO with a cubic sillenite single phase was prepared at the sintering process of 850 °C with a high relative sintered density of 96.82%. In situ and batch-type long-term conductivity measurements at 600 °C were carried out to verify the possible reason of degradation. Additional reduction-oxidation tests under CH₄ atmosphere by thermogravimetric analysis (TGA) revealed possible application temperature of 14BTO electrolytes below 700 °C.     

Application of sonochemical processing to LSC(La0.6Sr0.4CoO3)/SDC(Sm2O3-doped CeO2) composite cathodes for solid oxide fuel cells involving CeO2-based electrolytes

Nanocrystalline Sm₂O₃-Doped CeO₂ (SDC) powders were synthesized in a single- and two-phase material system by using sonochemical processing with high-frequency agitation. The synthesized SDC nanocrystalline powders were used to coat the mixed-conducting La_0.6Sr_0.4CoO₃ (LSC) cathode materials. The combined synthesis processing allows the artificial coating of the LSC materials with the ionic-conducting SDC electrolyte. The electrochemical polarizations of the SDC/LSC composites are characterized using a geometrically constricted contact between the ionic probe and the SDC/LSC composites. The lowest cathode polarization was obtained for the LSC (85 wt%)/SDC (15 wt%). The lowest electrode polarization is believed to result from the high density of the triple-phase boundaries when the constituent phases are interconnected in a 3-dimensional manner.     

Enhancing the performance and stability of solid oxide fuel cells by adopting samarium-doped ceria buffer layer

In this work, the Sm_0.2Ce_0.8O_1.9 (SDC) buffer layer was used to replace the Gd_0.1Ce_0.9O_1.95 (GDC) buffer layer to improve the long-term stability and performance of the solid oxide fuel cells (SOFCs) in the intermediate temperature (550–750 °C). The buffer layer was prepared by screen printing method. The micromorphology of the SDC buffer layer and the cell structures was observed by scanning electron microscopy (SEM). The electrochemical impedance spectroscopy (EIS) results showed that the polarization resistance (R_P) of the cell with SDC buffer layer was smaller than that of the cell with GDC buffer layer, reducing the R_P values by 43.52% and 43.33%, respectively (SDC-cell: 0.12 Ω cm² at 650 °C and 0.27 Ω cm² at 600 °C). The maximum power density of the cell with SDC buffer layer is 560 mW cm⁻² at 650 °C, which was 25% higher than that with GDC buffer layer. The long-term durability of the cell with SDC buffer layer was better than that of the cell with GDC buffer layer. These provide an excellent prospect for utilizing SDC buffer layer.     

Fabrication of electrolyte materials for solid oxide fuel cells by tape-casting

In this research, solid oxide fuel cell electrolytes were fabricated by aqueous tape-casting technique. The basic compositions for SOFC electrolyte systems were focused on yttria-stabilized zirconia (YSZ) system. The powders used in this study were from different sources. ZrO₂-based system doped with 3, 8, and 10 mol% of Y₂O₃, and 8YSZ electrolyte tape illustrated the desirable properties. The grain size of the sintered electrolyte tapes was in the range of 0.5–1 μm with 98–99% of theoretical density. Phase and crystal structure showed the pure cubic fluorite structure for 8–10 mol% YSZ and tetragonal phase for 3 mol% doped. The electrolyte tapes sintered at 1450 °C for 4 h had the highest ionic conductivity of 30.11 × 10⁻³ S/cm which was measured at 600 °C. The flexural strengths were in the range of 100–180 MPa for 8–10 mol% YSZ, and 400–680 MPa for 3 mol% YSZ.     

Synthesis of nanocrystalline 8 mol% yttria stabilized zirconia by the oleate complex route

Nanocrystalline 8 mol% yttria stabilized zirconia (YSZ) powder has been synthesized by the oleate complex route. Oleate complexes of zirconium and yttrium were formed in the hexane rich layer by the reaction of sodium oleate with zirconyl chloride and yttrium chloride at the interface of the two ternary solutions in water–ethanol–hexane system. The zirconyl oletae and yttrium oleate complexes on heating decomposed to oxide through the formation of carbonate intermediates. The powder obtained by calcination at 600 °C for 2 h was cubic YSZ with surface area of 42 m²/g. The YSZ powder contained primary particles of ∼300 nm size and the primary particles were aggregate of crystallites of 5–10 nm. The compacts prepared from the YSZ powder were sintered to ∼99% TD (theoretical density) at 1400 °C. The sintered YSZ had a low average grain size of 0.73 μm.     

Tailoring the properties of yttria-stabilized zirconia powders prepared by the sol-gel method for potential use in solid oxide fuel cells

Yttria-stabilized zirconia (YSZ) powders have been prepared by the sol-gel method, following two alternative procedures: a series of powders was obtained by drying the sol-gel solutions in air at 100 °C until dry residue, and another series of powders was obtained by scratching the thin films deposited on cylindrical wide flat glassy surfaces after evaporating to dryness in air at 100 °C for 2 h. Samples were characterized by Scanning Electron Microscopy (SEM), nitrogen adsorption at −196 °C and Fourier Transform Infrared (FT-IR) spectroscopy. In general, a noticeable contraction of the pores is observed as the molecular size of the alcohols used grows. Powders prepared by conventional drying of sol-gel solutions at 100 °C exhibit remarkably high values of specific surface area (up to 148 m² g^− 1). On the contrary, samples prepared by scratching of the deposited thin films show a noticeable decrease in their specific surface area. Values of fractal dimension follow the same trend and indicate that, in general, the texture of the samples is mainly microporous for the first series of samples and more ordered for the second one. Finally, in order to investigate the effect of the calcination temperature on the morphological and textural properties of 3 mol% yttria-stabilized zirconia powders, once the 3YSZ powders were dried at 100 °C they were subjected to calcination at different temperatures. The experimental results suggest that the removal of residual water and alcohol occluded within the powder particles as well as the elimination of gases produced during the calcination stage play a very important role in the development of the porosity and surface area of the samples.     

Synthesis and densification of lanthanum silicate apatite electrolyte for intermediate temperature solid oxide fuel cell via co-precipitation method

Lanthanum silicate apatite (LSA, La_9.33+xSi₆O_26+1.5x, x = 0–0.67) has been widely investigated as a promising electrolyte material for intermediate temperature solid oxide fuel cell (SOFC). In this work, a facile and low-cost co-precipitation method is used to synthesize LSA precursor powders. The well dispersed nanopowders (ca. 70 nm) with pure hexagonal LSA phase are obtained by calcining the precursor at 900 °C. Impurity of La₂SiO₅, caused by the different precipitation productivities of La(NO₃)₃ and TEOS, can be eliminated through lowering the La/Si ratio in the starting mixtures. The dispersant (PEG200) plays a crucial role in co-precipitation processes, which can effectively mitigate the agglomeration and therefore significantly improve the sinterability of the nanoparticles. Dense LSA ceramic with relative density of 98% is obtained after sintering at 1550 °C, which exhibits a conductivity of 0.13 mS cm⁻¹ at 500 °C.     

BSCF/GDC as a refined cathode to the single-chamber solid oxide fuel cell based on a LAMOX electrolyte

In an effort to build the solid oxide fuel cell for intermediate temperature operations, the oxide ion conductor member of LAMOX family appears to be an ideal candidate for electrolyte since its parent crystal La₂Mo₂O₉ shows a monoclinic-cubic phase transition around 580 °C. Nonetheless, members of the LAMOX family are much less refractory than the conventional electrode compositions which are targeted to coordinate with the electrolyte of yttrium stabilized zirconia. In this work, we study the viability of a cathode composite of Ba_0.5Sr₀₅Co_0.8Fe_0.2O₃ (BSCF) and gadolinium doped ceria (GDC) to match the electrolyte La_1.8Dy_0.2Mo₂O₉ (LDM). Severe interfacial reactions between BSCF and LDM require a ceria-based diffusion barrier between them. The iron-doped GDC barrier of high sinterability is a convenient choice to block the unwanted reactions, allowing us to devise a BSCF/GDC composite cathode of gradient GDC content to relieve thermal stresses. The cell, operated in a mixed reactant chamber with flowing methane/air, functions properly at operation temperature 625–700 °C. Its maximum power output is recorded at 675 °C, since the BSCF crystal begins to degrade at 700 °C under the methane/air atmosphere.     

Sr and Fe co-doped Ba2In2O5 as a new proton-conductor-derived cathode for proton-conducting solid oxide fuel cells

BaSrInFeO₅ (BSIF), a new cathode material for proton-conducting solid oxide fuel cells (SOFCs), is designed based on the modification of the Ba₂In₂O₅ proton conductor with Sr and Fe cations. Compared with the Ba₂In₂O₅ proton conductor tailored with only Fe cations (Ba₂InFeO₅, BIF), doping Sr can improve the chemical stability and also benefit the formation of oxygen vacancies. The proton mobility is also improved with Sr-doping, which is confirmed by first-principles calculations and experimental studies. An H-SOFC using the BSIF cathode generates a relatively high peak power density of 1192 mW cm^-2 at 700 ^oC, which is superior to many cells in previous reports. First-principles calculations find that the cathode oxygen reduction reaction (ORR) energy barrier for BSIF is significantly lower than that for BIF. Although Ba₂In₂O₅ is less studied, the derived cathode materials can still present decent performance, probably offering new material selections for H-SOFCs.     

Combining coal gasification, natural gas reforming, and solid oxide fuel cells for efficient polygeneration with CO2 capture and sequestration

Several polygeneration process systems are presented which convert natural gas and coal to gasoline, diesel, methanol, and electricity. By using solid oxide fuel cells as the primary electricity generator, the presented systems improve upon a recently introduced concept by which natural gas is reformed inside the radiant cooler of a gasifier. Simulations and techno-economic analyses performed for a wide range of process configurations and market conditions show that this strategy results in significant efficiency and profitability improvements when CO₂ capture and sequestration are employed. Market considerations for this analysis include variations in purchase prices of the coal and natural gas, sale prices of the products, and CO₂ emission tax rates.     

Synthesis, structural analysis and electrochemical performance of low-copper content La2Ni1−xCuxO4+δ materials as new cathodes for solid oxide fuel cells

In order to enhance the electrochemical performance of solid oxide fuel cells (SOFCs), La₂Ni_1−xCuO_4+δ (x = 0, 0.01, 0.02, 0.05 and 0.1) doped with copper in percentages, varying between 1% and 10%, were prepared following the modified Pechini method. The microstructure and morphology of the samples were analyzed by XRD and SEM. The electrochemical performance was followed by impedance spectroscopy. La₂Ni_0.99Cu_0.01O_4+δ samples showed good electrochemical and physicochemical properties with respect to the undoped material and is potentially a promising cathode. Indeed, doping with such small amounts of copper (1%) into the nickel site led to the formation of pure phases and stabilized the material before and after use at high temperature under air. In contrast, doping with higher amounts of copper (2%, 5% and 10%) led, after heating at 1000 °C for 48 h, to the formation of another phase resulting from the diffusion of copper into the YSZ electrolyte, limiting the interest to these materials as SOFC cathodes.     

Layered NdBaCo2−xNixO5+δ perovskite oxides as cathodes for intermediate temperature solid oxide fuel cells

The effect of Ni substitution on the crystal chemistry, thermal and electrochemical properties, and catalytic activity for oxygen reduction reaction of the layered NdBaCo_2−xNi_xO_5+δ perovskite oxides has been investigated for 0 ≤ x ≤ 0.6. The oxygen content (5 + δ) and oxidation state of the (Co, Ni) ions in the air-synthesized NdBaCo_2−xNi_xO_5+δ samples decrease with increasing Ni content, accompanied by a structural transition from tetragonal (0 ≤ x ≤ 0.4) to orthorhombic (x = 0.6). Similarly, the thermal expansion coefficient (TEC) and electrical conductivity also decrease with increasing Ni content. The x = 0.2 and 0.4 samples exhibit slightly improved performance as cathodes in single cell solid oxide fuel cell (SOFC) compared to the x = 0 sample, which is in accordance with the ac-impedance data. Among the samples studied, the x = 0.4 sample exhibits a combination of low thermal expansion and high catalytic activity for the oxygen reduction reaction in SOFC.     

Synthesis and characterization of CeO2 nano-rods

We report a synthesis of two types of CeO₂ nano-rods via the facile and efficient hydrothermal process free from any surfactant and template. The synthesized nano-rods are chemically identified as CeO₂ with the standard fluorite structure but their morphologies are different. The nano-rods prepared with cerium nitrate hexahydrate and sodium phosphate are thicker and shorter with diameter of ∼30 nm and length of ∼100 nm, and those prepared with cerium acetate hydrate and dibasic sodium phosphate are thinner and longer with ∼10 nm in diameter and ∼400 nm in length. Microstructural analyses reveal that the two species of nano-rods have low-energy {111} surfaces and grow along the 〈112〉 direction. As a consequence of their morphologies, the two types of synthesized nano-rods exhibit excellent UV-absorption ability in comparison to the irregular CeO₂ nanoparticles.     

A polymeric solid electrolyte based on a binary blend of poly(ethylene oxide), poly(methyl vinyl ether-maleic acid) and LiClO4

A new polymeric solid electrolyte based on a PEO/PMVE-MAc blend, complexed with LiClO₄, was obtained and characterized by differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), polarized light optical microscopy, electrochemical impedance and cyclic voltammetry. DSC traces indicated miscibility for all the PSE samples. Crystallinity was suppressed for samples with LiClO₄ concentrations higher than 2.5 wt%. FTIR associated with DSC studies indicated that there is a preferential formation of complexes PEO/Li⁺/PMVE-MAc in all PSE samples studied here. The ionic conductivity of PSE reaches a maximum of about 10⁻⁵ S/cm at ambient temperature and 7.5 wt% LiClO₄. The electrochemical stability window is 4.5 V and associated with the other characteristics, make the PSE studied here suitable for applications in ‘smart-windows’, batteries, sensors, etc.