CO2 and steam electrolysis using a microtubular solid oxide cell

Nickel-yttria stabilized zirconia (Ni-YSZ) supported tubes were fabricated by plastic extrusion molding (PEM). YSZ was used as the electrolyte and LSM-YSZ (lanthanum-strontium doped manganite) as the oxygen electrode. Both layers were deposited by dip coating and were then sintered at 1500 degrees C and 1150 degrees C, respectively. Coelectrolysis experiments were performed in these cells at 850 degrees C, using different fuel gas conditions varying the amount of steam, carbon dioxide, nitrogen and hydrogen. Area specific resistance (ASR) values ranged from 0.47 Omega cm(2), when rich steam and CO2 flows are used, to 1.74 Omega cm(2), when a diluted composition is used. Gas chromatography was used to examine the amount of H-2 and CO in the output gas. The obtained results are consistent with the equilibrium of the water gas shift reaction. For all the different analysed conditions, faradaic efficiency was found to be close to 100%. This experiment confirmed that there is no electronic conduction taking place through the YSZ electrolyte. The threshold for electronic conduction in the diluted feeding conditions (Poor H2O and CO2) for these particular YSZ-based cell was found at voltages of about 1.65 V

Reversible operation performance of microtubular solid oxide cells with a nickelate-based oxygen electrode

This paper describes the reversible operation of a highly efficient microtubular solid oxide cell (SOC) with a nickelate-based oxygen electrode. The fuel cell was composed of a microtubular support of nickel and yttria stabilized zirconia (Ni-YSZ), an YSZ dense electrolyte, and a double oxygen electrode formed by a first composite layer of praseodymium nickelate (PNO) and gadolinium-doped ceria (CGO) and a second one of PNO. A good performance of the cell was obtained at temperatures up to 800 °C for both fuel cell (SOFC) and electrolysis (SOEC) operation modes, specially promising in electrolysis mode. The current density in SOEC mode at 800 °C is about -980 mA cm-2 at 1.2V with 50% steam. Current density versus voltage curves (j-V) present a linear behavior in the electrolysis mode, with a specific cell area resistance (ASR) of 0.32 O cm-2. Durability experiments were carried out switching the voltage from 0.7V to 1.2V. No apparent degradation was observed in fuel cell mode and SOEC mode up to a period of about 100 h. However, after this period especially in electrolysis mode there is an accumulated degradation associated to nickel coarsening, as confirmed by SEM and EIS experiments. Those results confirm that nickelate based oxygen electrodes are excellent candidates for reversible SOCs. © 2019 Hydrogen Energy Publications LL

Lanthanide nickelates for their application on Solid Oxide Cells

High-temperature technologies like solid oxide cells (SOC) have been employed to provide power-to-fuel and vice versa for energy conversion and storage. These technologies are a work in progress due to durability and compatibility issues between components at high temperatures. For this reason, the pursuit of optimal physical, mechanical, and chemical properties of SOC materials at lower temperatures has become more diligent. Finding suitable air electrodes has become one of the more notable obstacles to complete implementation in the industry. One of the most recent alternatives is the use of lanthanide nickelates with the Ruddlesden-Popper (RP), Lnn+1NinO3n±1 (Ln = La, Nd or Pr), and perovskite, LnNiO3-δ, structures. These materials present fast ionic and electronic transport, as well as flexible oxygen stoichiometry that makes them compelling for this purpose. As part of an ongoing study on alternative air electrode advanced materials, this review is focused on documenting the relevant findings of RP nickelates over the years, especially focusing on the current status in research and development while comparing the electrochemical performance of nickelate air electrodes

Direct-methane anode-supported solid oxide fuel cells fabricated by aqueous gel-casting

Direct methane Solid Oxide Fuel Cells (SOFCs) operated under catalytic partial oxidation (CPOX) conditions are investigated, focusing on the processing of the anode support and the anode deactivation caused by carbon deposition. Anode-supported SOFCs based on gadolinium-doped ceria (GDC) electrolyte, and NiO-GDC anode support were fabricated by the gel-casting method. Suitable aqueous slurries formulations of NiO–GDC were prepared, starting NiO-GDC nanocomposite powders, agarose as gelling agent and rice starch as pore former. Electrochemical and mechanical tests evidenced that the support of 550 ± 50 µm thickness and 10 wt% pore former is a good candidate for direct-methane SOFCs. The cells operating under stoichiometric conditions of CPOX reached a performance of 0.64 W·cm−2 at 650 ºC, a very close value to that measured under humidified hydrogen (0.71 W·cm−2). The best electrochemical stability of the cell is achieved at a CH4/O2 ratio of 2.5, showing no evidence of carbon deposition and reducing nickel re-oxidation significantly

Incorporation of nio into sio2, tio2, al2o3, and na4.2ca2.8(si6o18) matrices: Medium effect on the optical properties and catalytic degradation of methylene blue

The medium effect of the optical and catalytic degradation of methylene blue was studied in the NiO/SiO2, NiO/TiO2, NiO/Al2O3, and NiO/Na4.2Ca2.8(Si6O18) composites, which were prepared by a solid-state method. The new composites were characterized by XRD (X-ray diffraction of powder), SEM/EDS, TEM, and HR-TEM. The size of the NiO nanoparticles obtained from the PSP-4-PVP (polyvinylpyrrolidone) precursors inside the different matrices follow the order of SiO2 > TiO2 > Al2O3 . However, NiO nanoparticles obtained from the chitosan precursor does not present an effect on the particle size. It was found that the medium effect of the matrices (SiO2, TiO2, Al2O3, and Na4.2Ca2.8(Si6O18)) on the photocatalytic methylene blue degradation, can be described as a specific interaction of the NiO material acting as a semiconductor with the MxOy materials through a possible p-n junction. The highest catalytic activity was found for the TiO2 and glass composites where a favorable p-n junction was formed. The isolating character of Al2O3 and SiO2 and their non-semiconductor behavior preclude this interaction to form a p-n junction, and thus a lower catalytic activity. NiO/SiO2 and NiO/Na4.2Ca2.8(Si6O18) showed a similar photocatalytic behavior. On the other hand, the effect of the matrix on the optical properties for the NiO/SiO2, NiO/TiO2, NiO/Al2O3, and NiO/Na4.2Ca2.8(Si6O18) composites can be described by the different dielectric constants of the SiO2, TiO2, Al2O3, Na4.2Ca2.8(Si6O18) matrices. The maxima absorption of the composites (¿max) exhibit a direct relationship with the dielectric constants, while their semiconductor bandgap (Eg) present an inverse relationship with the dielectric constants. A direct relationship between ¿max and Eg was found from these correlations. The effect of the polymer precursor on the particle size can explain some deviations from this relationship, as the correlation between the particle size and absorption is well known. Finally, the NiO/Na4.2Ca2.8(Si6O18) composite was reported in this work for the first time

Cation-driven electrical conductivity in Ta-doped orthorhombic zirconia ceramics

This paper is devoted to the study of the electrical conductivity of tantalum-doped zirconia ceramics prepared by spark plasma sintering. In this study, the temperature dependence of conductivity in as-prepared specimens and in those previously annealed in air is determined and compared. A semi-empirical model, which is based on the oxidation states of the cations, has been developed and successfully assessed. According to this, the conductivity is basically controlled by the diffusion of tetravalent zirconium cations in both cases, although the concentration of these species varies drastically with the amount of induced oxygen vacancies. This is a quite unexpected fact, since conductivity is normally controlled by anionic diffusion in zirconia ceramics. This option is forbidden here due to the presence of substitutional pentavalent cations. Therefore, conductivity values are much lower than those reported in trivalent or divalent substitutional cation doped zirconia ceramics

Optimization of laser-patterned YSZ-LSM composite cathode-electrolyte interfaces for solid oxide fuel cells

Patterned cathode/electrolyte interfaces formed by a hexagonal array of ~22 µm deep wells with 24 µm lattice parameter have been prepared by pulsed laser machining to enlarge the contact surface and, consequently, to reduce the cathode polarization of Solid Oxide Fuel Cells. These new interfaces have been tested in YSZ-LSM/YSZ/YSZ-LSM symmetrical cells, where the cathode is deposited by dip-coating. Appropriate ceramic suspensions have been formulated to penetrate into deep wells without presenting interfacial delamination after sintering. We analyse their applicability by comparing their rheology with the microstructure and electrochemical performance of the cells. The activation component of the polarization resistance is reduced by ~50% using ethanol-based suspensions with 20 wt% solids loading, although the gas diffusion component increases due to excessive densification. Alternative ceramic suspensions with 17.5 wt% solids loading provide optimum electrode gas diffusion but lower activation components, resulting in an overall decrease of ~20% in polarization resistance

The effect of pore-former morphology on the electrochemical performance of solid oxide fuel cells under combined fuel cell and electrolysis modes

The effect of the pore-former used in the Ni-YSZ fuel electrode on the electrochemical performance of solid oxide cells is studied. Three cells with the configuration of Ni-YSZ/YSZ/Nd2NiO4+d-YSZ were fabricated with different pore-formers, such as graphite, PMMA (polymethyl methacrylate) or an equal mixture of both, which were added to the Ni-YSZ support during the fabrication process. The results show that the Ni-YSZ support containing graphite leads to a more porous support and formation of coarser pores in the vicinity of the electrolyte. This leads to a reduction in the triple phase boundary (TPB) length with a corresponding increase of activation polarization and, as a consequence, the overall cell performance decreases in both fuel cell and electrolysis modes. The cell having PMMA delivered the highest performance under both operation modes (818 and -713 mAcm-2 were obtained in SOFC and SOEC modes at 800 °C), due to finer pores next to the electrolyte. The cell having the mixture of both pore-formers delivered intermediate results. All the cells show similar concentration polarization values meaning that even the least porous cell (PMMA) provided sufficient porosity for gas flow. In addition, long term reversible experiments were performed, showing no degradation for a period above 400 h

Tecnologías del hidrógeno

El interés por las tecnologías del hidrógeno ha crecido en los últimos años, principalmente porque una economía basada en el hidrógeno puede dar respuesta a los grandes desafíos de la economía global del futuro: seguridad energética y cambio climático. Aprovechando este impulso, cada vez son más los países que están implementando un número creciente de políticas en favor del hidrógeno. Prueba de ello es la Estrategia Europea del Hidrógeno que establece al hidrógeno como un elemento esencial en| la descarbonización total del actual sistema energético para alcanzar el compromiso de la UE con la neutralidad de carbono en 2050. No obstante, el desarrollo exitoso de las tecnologías del hidrógeno requiere que todos los actores, incluidos los sectores público y privado, aumenten sus esfuerzos para acelerar su despliegue y hacer que su implantación a gran escala resulte competitiva. Los grupos de investigación que forman parte del área de trabajo de tecnologías del hidrógeno, dentro de la Plataforma Temática Interdisciplinar PTI Mobility 2030 del CSIC, trabajan en este sentido, desarrollando su labor en áreas tan diversas como la generación, el almacenamiento, la distribución y los usos del hidrógeno. The interest in hydrogen technologies has grown in recent years, mainly because an economy based on hydrogen can help to solve important challenges related to the global economy of the future: energy security and climate change. Taking advantage of this momentum, more and more countries are implementing a growing number of policies related to hydrogen. Indeed, the European Hydrogen Strategy establishes hydrogen as essential drivers for the total decarbonization of the current energy system in order to achieve the Ells commitment related to carbon neutrality by 2050. However, the successful development of the hydrogen technologies requires the collaboration of the public and private sectors to accelerate its deployment and make more competitive its implementation at large-scale. The research groups that take part of the line of work dedicated to hydrogen technologies, within the CSIC Interdisciplinary Thematic Platform PTI Mobility 2030, work in this regard, developing their investigations in several important areas related to the hydrogen technologies such as hydrogen generation, storage, distribution and uses