Unravelling the role of dopants in the electrocatalytic activity of ceria towards CO reduction in solid oxide electrolysis cells.

CO reduction in Solid Oxide Electrolysis Cells (SOECs) is a key-technology for the transition to a sustainable energy infrastructure and chemical industry. Ceria (CeO) holds great promise in developing highly efficient, cost-effective and durable fuel electrodes, due to its promising electrocatalytic properties, and proven ability to suppress carbon deposition and to tolerate high concentrations of impurities. In the present work, we investigate the intrinsic electrocatalytic activity of ceria towards CO reduction by means of electrochemical impedance spectroscopy (EIS) on model systems with well-defined geometry, composition and surface area.

Passivation and activation of LaSrFeO thin film electrodes.

The oxygen exchange activity of thin dense LaSrFeO electrodes prepared by pulsed laser deposition was investigated by electrochemical impedance spectroscopy and electrical conductivity relaxation below 600 °C. The value of the surface exchange coefficient (k) measured at 491 °C decreased from an initial 4.4 × 10 cm s to 1.

Properties and Structure of the LiCl-films on Lithium Anodes in Liquid Cathodes.

Lithium anodes passivated by LiCl layers in different types of liquid cathodes (catholytes) based on LiAlCl4 in SOCl2 or SO2 have been studied by means of impedance spectroscopy. The impedance spectra have been fitted with two equivalent circuits using a nonlinear least squares fit program. Information about the ionic conductivity and the structure of the layers has been extracted.

Understanding the processes governing performance and durability of solid oxide electrolysis cells.

Operation of a Ni-YSZ electrode supported Solid Oxide Cell (SOC) was studied in both fuel cell mode (FC-mode) and electrolysis cell mode (EC-mode) in mixtures of H2O/H2, CO2/CO, H2O/H2O/CO2/CO at 750 °C, 800 °C and 850 °C. Although the SOCs are reversible, the polarisation characterisation shows that the kinetics for the reduction of H2O and CO2 is slower compared to oxidation of H2 and CO, and that oxidation/reduction in CO2/CO mixtures is slower than in H2O/H2 mixtures. The kinetic differences are partly related to the polarisation heating and the entropy change.

Kinetics of CO/CO2 and H2/H2O reactions at Ni-based and ceria-based solid-oxide-cell electrodes.

The solid oxide electrochemical cell (SOC) is an energy conversion technology that can be operated reversibly, to efficiently convert chemical fuels to electricity (fuel cell mode) as well as to store electricity as chemical fuels (electrolysis mode). The SOC fuel-electrode carries out the electrochemical reactions CO2 + 2e(-) ↔ CO + O(2-) and H2O + 2e(-) ↔ H2 + O(2-), for which the electrocatalytic activities of different electrodes differ considerably. The relative activities in CO/CO2 and H2/H2O and the nature of the differences are not well studied, even for the most common fuel-electrode material, a composite of nickel and yttria/scandia stabilized zirconia (Ni-SZ).

Eliminating degradation in solid oxide electrochemical cells by reversible operation.

One promising energy storage technology is the solid oxide electrochemical cell (SOC), which can both store electricity as chemical fuels (electrolysis mode) and convert fuels to electricity (fuel-cell mode). The widespread use of SOCs has been hindered by insufficient long-term stability, in particular at high current densities. Here we demonstrate that severe electrolysis-induced degradation, which was previously believed to be irreversible, can be completely eliminated by reversibly cycling between electrolysis and fuel-cell modes, similar to a rechargeable battery.

TOF-SIMS characterization of impurity enrichment and redistribution in solid oxide electrolysis cells during operation.

TOF-SIMS analyses of state-of-the-art high temperature solid oxide electrolysis cells before and after testing under different operating conditions were performed. The investigated cells consist of an yttria stabilized zirconia (YSZ) electrolyte, a La1-xSrxMnO3-δ composite anode and a Ni-YSZ cermet cathode. The surfaces and cross-sections of the cells were analyzed, and several elemental impurities like Si, Ca and Na were identified and spatially mapped and their enrichment and migration during operation is reported.

Generalized trends in the formation energies of perovskite oxides.

Generalized trends in the formation energies of several families of perovskite oxides (ABO3) and plausible explanations to their existence are provided in this study through a combination of DFT calculations, solid-state physics analyses and simple physical/chemical descriptors. The studied elements at the A site of perovskites comprise rare-earth, alkaline-earth and alkaline metals, whereas 3d and 5d metals were studied at the B site. We also include ReO3-type compounds, which have the same crystal structure of cubic ABO3 perovskites except without A-site elements.

Origin of electrolyte-dopant dependent sulfur poisoning of SOFC anodes.

The mechanisms governing the sulfur poisoning of the triple phase boundary (TPB) of Ni-XSZ (X2O3 stabilized zirconia) anodes have been investigated using density functional theory. The calculated sulfur adsorption energies reveal a clear correlation between the size of the cation dopant X(3+) and the sulfur tolerance of the Ni-XSZ anode; the smaller the ionic radius, the higher the sulfur tolerance. The mechanistic study shows that the size of X(3+) strongly influences XSZ's surface energy, which in turn determines the adhesion of Ni to XSZ.