Nb5+-Doped SrCoO3-δ Perovskites as Potential Cathodes for Solid-Oxide Fuel Cells.
ABSTRACT: SrCoO3-δ outperforms as cathode material in solid-oxide fuel cells (SOFC) when the three-dimensional (3C-type) perovskite structure is stabilized by the inclusion of highly-charged transition-metal ions at the octahedral positions. In a previous work we studied the Nb incorporation at the Co positions in the SrCo1-xNbxO3-δ system, in which the stabilization of a tetragonal P4/mmm perovskite superstructure was described for the x = 0.05 composition. In the present study we extend this investigation to the x = 0.10-0.15 range, also observing the formation of the tetragonal P4/mmm structure instead of the unwanted hexagonal phase corresponding to the 2H polytype. We also investigated the effect of Nb5+ doping on the thermal, electrical, and electrochemical properties of SrCo1-xNbxO3-δ (x = 0.1 and 0.15) perovskite oxides performing as cathodes in SOFC. In comparison with the undoped hexagonal SrCoO3-δ phase, the resulting compounds present high thermal stability and an increase of the electrical conductivity. The single-cell tests for these compositions (x = 0.10 and 0.15) with La0.8Sr0.2Ga0.83Mg0.17O3-δ (LSGM) as electrolyte and SrMo0.8Fe0.2CoO3-δ as anode gave maximum power densities of 693 and 550 mW∙cm-2 at 850 °C respectively, using pure H₂ as fuel and air as oxidant.
Project description:In the aim to stabilize novel three-dimensional perovskite oxides based upon SrCoO3-δ, we have designed and prepared SrCo1-xRexO3-δ phases (x = 0.05 and 0.10), successfully avoiding the competitive hexagonal 2H polytypes. Their performance as cathode materials in intermediate-temperature solid oxide fuel cells (IT-SOFC) has been investigated. The characterization of these oxides included X-ray (XRD) and in situ temperature-dependent neutron powder diffraction (NPD) experiments for x = 0.10. At room temperature, SrCo1-xRexO3-δ perovskites are defined in the P4/mmm space group, which corresponds to a subtle tetragonal perovskite superstructure with unit-cell parameters a = b ≈ ao, c = 2ao (ao = 3.861 and 3.868 Å, for x = 0.05 and 0.10, respectively). The crystal structure evolves above 380 °C to a simple cubic perovskite unit cell, as observed from in-situ NPD data. The electrical conductivity gave maximum values of 43.5 S·cm-1 and 51.6 S·cm-1 for x = 0.05 and x = 0.10, respectively, at 850 °C. The area specific resistance (ASR) polarization resistance determined in symmetrical cells is as low as 0.087 Ω·cm² and 0.065 Ω·cm² for x = 0.05 and x = 0.10, respectively, at 850 °C. In single test cells these materials generated a maximum power of around 0.6 W/cm² at 850 °C with pure H₂ as a fuel, in an electrolyte-supported configuration with La0.8Sr0.2Ga0.83Mg0.17O3-δ (LSGM) as the electrolyte. Therefore, we propose the SrCo1-xRexO3-δ (x = 0.10 and 0.05) perovskite oxides as promising candidates for cathodes in IT-SOFC.
Project description:The effect of the A-site cation ordering on the chemical stability, oxygen stoichiometry and electrical conductivity in layered LaBaCo₂O5+δ double perovskite was studied as a function of temperature and partial pressure of oxygen. Tetragonal A-site cation ordered layered LaBaCo₂O5+δ double perovskite was obtained by annealing cubic A-site cation disordered La0.5Ba0.5CoO3-δ perovskite at 1100 °C in N₂. High temperature X-ray diffraction between room temperature (RT) and 800 °C revealed that LaBaCo₂O5+δ remains tetragonal during heating in oxidizing atmosphere, but goes through two phase transitions in N₂ and between 450 °C and 675 °C from tetragonal P4/mmm to orthorhombic Pmmm and back to P4/mmm due to oxygen vacancy ordering followed by disordering of the oxygen vacancies. An anisotropic chemical and thermal expansion of LaBaCo₂O5+δ was demonstrated. La0.5Ba0.5CoO3-δ remained cubic at the studied temperature irrespective of partial pressure of oxygen. LaBaCo₂O5+δ is metastable with respect to La0.5Ba0.5CoO3-δ at oxidizing conditions inferred from the thermal evolution of the oxygen deficiency and oxidation state of Co in the two materials. The oxidation state of Co is higher in La0.5Ba0.5CoO3-δ resulting in a higher electrical conductivity relative to LaBaCo₂O5+δ. The conductivity in both materials was reduced with decreasing partial pressure of oxygen pointing to a p-type semiconducting behavior.
Project description:The high-temperature phase behaviour of the ferroelectric layered perovskite Bi4Ti3O12 has been re-examined by high-resolution powder neutron diffraction. Previous studies, both experimental and theoretical, had suggested conflicting structural models and phase transition sequences, exacerbated by the complex interplay of several competing structural instabilities. This study confirms that Bi4Ti3O12 undergoes two separate structural transitions from the aristotype tetragonal phase (space group I4/mmm) to the ambient-temperature ferroelectric phase (confirmed as monoclinic, B1a1). An unusual, and previously unconsidered, intermediate paraelectric phase is suggested to exist above T C with tetragonal symmetry, space group P4/mbm. This phase is peculiar in displaying a unique type of octahedral tilting, in which the triple perovskite blocks of the layered structure alternate between tilted and untilted. This is rationalized in terms of the bonding requirements of the Bi3+ cations within the perovskite blocks.
Project description:SrMo1-xMxO3-δ (M = Fe and Cr, x = 0.1 and 0.2) oxides have been recently described as excellent anode materials for solid oxide fuel cells at intermediate temperatures (IT-SOFC) with LSGM as the electrolyte. In this work, we have improved their properties by doping with aliovalent Mg ions at the B-site of the parent SrMoO₃ perovskite. SrMo1-xMgxO3-δ (x = 0.1, 0.2) oxides have been prepared, characterized and tested as anode materials in single solid-oxide fuel cells, yielding output powers near 900 mW/cm-2 at 850 °C using pure H₂ as fuel. We have studied its crystal structure with an "in situ" neutron power diffraction (NPD) experiment at temperatures as high as 800 °C, emulating the working conditions of an SOFC. Adequately high oxygen deficiencies, observed by NPD, together with elevated disk-shaped anisotropic displacement factors suggest a high ionic conductivity at the working temperatures. Furthermore, thermal expansion measurements, chemical compatibility with the LSGM electrolyte, electronic conductivity and reversibility upon cycling in oxidizing-reducing atmospheres have been carried out to find out the correlation between the excellent performance as an anode and the structural features.
Project description:Development of chemically stable proton conductors for solid oxide fuel cells (SOFCs) will solve several issues, including cost associated with expensive inter-connectors, and long-term durability. Best known Y-doped BaCeO3 (YBC) proton conductors-based SOFCs suffer from chemical stability under SOFC by-products including CO2 and H2O. Here, for the first time, we report novel perovskite-type Ba0.5Sr0.5Ce0.6Zr0.2Gd0.1Y0.1O3-? by substituting Sr for Ba and co-substituting Gd + Zr for Ce in YBC that showed excellent chemical stability under SOFC by-products (e.g., CO2 and H2O) and retained a high proton conductivity, key properties which were lacking since the discovery of YBCs. In situ and ex- situ powder X-ray diffraction and thermo-gravimetric analysis demonstrate superior structural stability of investigated perovskite under SOFC by-products. The electrical measurements reveal pure proton conductivity, as confirmed by an open circuit potential of 1.15?V for H2-air cell at 700°C, and merits as electrolyte for H-SOFCs.
Project description:Development of alternative ceramic oxide anode materials is a key step for direct hydrocarbon solid oxide fuel cells (SOFCs). Several lanthanide based layered perovskite-structured oxides demonstrate outstanding oxygen diffusion rate, favorable electronic conductivity, and good oxygen surface exchange kinetics, owing to A-site ordered structure in which lanthanide and alkali-earth ions occupy alternate (001) layers and oxygen vacancies are mainly located in [LnOx] planes. Here we report a nickel-free cation deficient layered perovskite, (PrBa)0.95(Fe0.9Mo0.1)2O5 + ? (PBFM), for SOFC anode, and this anode shows an outstanding performance with high resistance against both carbon build-up and sulfur poisoning in hydrocarbon fuels. At 800?°C, the layered PBFM showed high electrical conductivity of 59.2 S cm(-1) in 5% H2 and peak power densities of 1.72 and 0.54 W cm(-2) using H2 and CH4 as fuel, respectively. The cell exhibits a very stable performance under a constant current load of 1.0 A cm(-2). To our best knowledge, this is the highest performance of ceramic anodes operated in methane. In addition, the anode is structurally stable at various fuel and temperature conditions, suggesting that it is a feasible material candidate for high-performing SOFC anode.
Project description:Solid oxide fuel cells (SOFC) are the cleanest, most efficient, and cost-effective option for direct conversion to electricity of a wide variety of fuels. While significant progress has been made in anode materials with enhanced tolerance to coking and contaminant poisoning, cathodic polarization still contributes considerably to energy loss, more so at lower operating temperatures. Here we report a synergistic effect of co-doping in a cation-ordered double-perovskite material, PrBa0.5Sr0.5Co(2-x)Fe(x)O(5+?), which has created pore channels that dramatically enhance oxygen ion diffusion and surface oxygen exchange while maintaining excellent compatibility and stability under operating conditions. Test cells based on these cathode materials demonstrate peak power densities ~2.2 W cm(-2) at 600°C, representing an important step toward commercially viable SOFC technologies.
Project description:Solid oxide fuel cells (SOFCs), which can directly convert chemical energy stored in fuels into electric power, represent a useful technology for a more sustainable future. They are particularly attractive given that they can be easily integrated into the currently available fossil fuel infrastructure to realize an ideal clean energy system. However, the widespread use of the SOFC technology is hindered by sulfur poisoning at the anode caused by the sulfur impurities in fossil fuels. Therefore, improving the sulfur tolerance of the anode is critical for developing SOFCs for use with fossil fuels. Herein, a novel, highly active, sulfur-tolerant anode for intermediate-temperature SOFCs is prepared via a facile impregnation and limited reaction protocol. During synthesis, Ni nanoparticles, water-storable BaZr0.4Ce0.4Y0.2O3-? (BZCY) perovskite, and amorphous BaO are formed in situ and deposited on the surface of a Sm0.2Ce0.8O1.9 (SDC) scaffold. More specifically, a porous SDC scaffold is impregnated with a well-designed proton-conducting perovskite oxide liquid precursor with the nominal composition of Ba(Zr0.4Ce0.4Y0.2)0.8Ni0.2O3-? (BZCYN), calcined and reduced in hydrogen. The as-synthesized hierarchical architecture exhibits high H2 electro-oxidation activity, excellent operational stability, superior sulfur tolerance, and good thermal cyclability. This work demonstrates the potential of combining nanocatalysts and water-storable materials in advanced electrocatalysts for SOFCs.
Project description:Interest in low-temperature operation of solid oxide fuel cells is growing. Recent advances in perovskite phases have resulted in an efficient H+/O2-/e- triple-conducting electrode BaCo0.4Fe0.4Zr0.1Y0.1O3-δ for low-temperature fuel cells. Here, we further develop BaCo0.4Fe0.4Zr0.1Y0.1O3-δ for electrolyte applications by taking advantage of its high ionic conduction while suppressing its electronic conduction through constructing a BaCo0.4Fe0.4Zr0.1Y0.1O3-δ-ZnO p-n heterostructure. With this approach, it has been demonstrated that BaCo0.4Fe0.4Zr0.1Y0.1O3-δ can be applied in a fuel cell with good electrolyte functionality, achieving attractive ionic conductivity and cell performance. Further investigation confirms the hybrid H+/O2- conducting capability of BaCo0.4Fe0.4Zr0.1Y0.1O3-δ-ZnO. An energy band alignment mechanism based on a p-n heterojunction is proposed to explain the suppression of electronic conductivity and promotion of ionic conductivity in the heterostructure. Our findings demonstrate that BaCo0.4Fe0.4Zr0.1Y0.1O3-δ is not only a good electrode but also a highly promising electrolyte. The approach reveals insight for developing advanced low-temperature solid oxide fuel cell electrolytes.
Project description:The perovskite Li0.2Na0.8NbO3 is shown, by powder neutron diffraction, to display a unique sequence of phase transitions at elevated temperature. The ambient temperature polar phase (rhombohedral, space group R3c) transforms via a first-order transition to a polar tetragonal phase (space group P42mc) in the region 150-300°C; these two phases correspond to Glazer tilt systems a-a-a- and a+a+c-, respectively. At 500°C a ferroelectric-paraelectric transition takes place from P42mc to P42/nmc, retaining the a+a+c- tilt. Transformation to a single-tilt system, a0a0c+ (space group P4/mbm), occurs at 750°C, with the final transition to the aristotype cubic phase at 850°C. The P42mc and P42/nmc phases have each been seen only once and twice each, respectively, in perovskite crystallography, in each case in compositions prepared at high pressure.