Christopher R. Graves

Poisoning of Solid Oxide Electrolysis Cells by Impurities

Electrolysis of H 2 0, CO 2 , and co-electrolysis of H 2 O and CO 2 was studied in Ni/yttria-stabilized zirconia (YSZ) electrode supported solid oxide electrolysis cells (SOECs) consisting of a Ni/YSZ support, a Ni/YSZ electrode layer, a YSZ electrolyte, and an lanthanum strontium manganite (LSM)/YSZ oxygen electrode When applying the gases as received, the cells degraded significantly at the Ni/YSZ electrode, whereas only minor (and initial) degradation was observed for either the Ni/YSZ or LSM/YSZ electrode. Application of clean gases to the Ni/YSZ electrode resulted in operation without any long-term degradation, in fact some cells activated slightly. This shows that the durability of these SOECs is heavily influenced by impurities in the inlet gases. Cleaning the inlet gases to the Ni/YSZ electrode may be a solution for operating these Ni/YSZ-based SOECs without long-term degradation.

Molybdate Based Ceramic Negative-Electrode Materials for Solid Oxide Cells

Novel molybdate materials with varying Mo valence were synthesized as possible negative-electrode materials for solid oxide cells. The phase, stability, microstructure and electrical conductivity were characterized. The electrochemical activity for H2O and CO2 reduction and H2 and CO oxidation was studied using simplified geometry point-contact electrodes. Unique phenomena were observed for some of the materials – they decomposed into multiple phases and formed a nanostructured surface upon exposure to operating conditions (in certain reducing atmospheres). The new phases and surface features enhanced the electrocatalytic activity and electronic conductivity. The polarization resistances of the best molybdates were two orders of magnitude lower than that of donor-doped strontium titanates. Many of the molybdate materials were significantly activated by cathodic polarization, and they exhibited higher performance for cathodic (electrolysis) polarization than for anodic (fuel cell) polarization, which makes them especially interesting for use in electrolysis electrodes.

Integrating Steel Production with Mineral Carbon Sequestration

The objectives of the project were (i) to develop a combination iron oxide production and carbon sequestration plant that will use serpentine ores as the source of iron and the extraction tailings as the storage element for CO2 disposal, (ii) the identification of locations within the US where this process may be implemented and (iii) to create a standardized process to characterize the serpentine deposits in terms of carbon disposal capacity and iron and steel production capacity. The first objective was not accomplished. The research failed to identify a technique to accelerate direct aqueous mineral carbonation, the limiting step in the integration of steel production and carbon sequestration. Objective (ii) was accomplished. It was found that the sequestration potential of the ultramafic resource surfaces in the US and Puerto Rico is approximately 4,647 Gt of CO2 or over 500 years of current US production of CO2. Lastly, a computer model was developed to investigate the impact of various system parameters (recoveries and efficiencies and capacities of different system components) and serpentinite quality as well as incorporation of CO2 from sources outside the steel industry.

Aspects of Metal-YSZ Electrode Kinetics Studied using Model Electrodes

The electrode kinetics of oxidation and reduction of H2/H2O and CO/CO2 at the metal/yttria stabilized zirconia (YSZ) interface were studied using model metal wire electrodes contacting polished YSZ pellets. The intent was to probe the reaction mechanisms by comparing the same reactions using different metals (Ag, Au, Cu, Ni, Pd, and Pt) under identical conditions relevant to fuel cell and electrolysis cell operation (e.g. including 50% H2/H2O and 50% CO/CO2). Impedance spectra were measured at open-circuit voltage and under polarization, and polarization sweeps were performed. The gas composition and temperature were varied to examine how the electrochemical measurements varied, to facilitate identifying the electrode rate-limiting processes. Possible mechanisms that may explain these and other details are discussed.