Kevin Blinn

Enhanced Sulfur and Coking Tolerance of a Mixed Ion Conductor for SOFCs: BaZr0.1Ce0.7Y0.2–xYbxO3–δ

Cleaning Solid Oxide Fuel Cells Solid oxide fuel cells, which operate between 500° and 1000°C, transport oxygen through a ceramic material. At these temperatures, metals that catalyze hydrocarbon reforming reactions can also be incorporated so that conventional fuels such as methane can power the cell. One problem, however, has been rapid deactivation by sulfur impurities and carbon buildup. Yang et al. (p. 126; see the Perspective by Selman) report that doping of a barium zirconate-cerate with the rare-earths Y and Yb creates a material that transports both protons and oxygen ions at 750°C. This material, when used with nickel at the fuel cell anode, resists deactivation even when traces of hydrogen sulfide are present, apparently through enhanced ability to supply or remove water during surface reactions. A barium zirconate-cerate doped with yttrium and ytterbium can transport both protons and oxygen ions at high temperatures. The anode materials that have been developed for solid oxide fuel cells (SOFCs) are vulnerable to deactivation by carbon buildup (coking) from hydrocarbon fuels or by sulfur contamination (poisoning). We report on a mixed ion conductor, BaZr0.1Ce0.7Y0.2–xYbxO3–δ, that allows rapid transport of both protons and oxide ion vacancies. It exhibits high ionic conductivity at relatively low temperatures (500° to 700°C). Its ability to resist deactivation by sulfur and coking appears linked to the mixed conductor’s enhanced catalytic activity for sulfur oxidation and hydrocarbon cracking and reforming, as well as enhanced water adsorption capability.

Promotion of water-mediated carbon removal by nanostructured barium oxide/nickel interfaces in solid oxide fuel cells.

The existing Ni-yttria-stabilized zirconia anodes in solid oxide fuel cells (SOFCs) perform poorly in carbon-containing fuels because of coking and deactivation at desired operating temperatures. Here we report a new anode with nanostructured barium oxide/nickel (BaO/Ni) interfaces for low-cost SOFCs, demonstrating high power density and stability in C3H8, CO and gasified carbon fuels at 750°C. Synchrotron-based X-ray analyses and microscopy reveal that nanosized BaO islands grow on the Ni surface, creating numerous nanostructured BaO/Ni interfaces that readily adsorb water and facilitate water-mediated carbon removal reactions. Density functional theory calculations predict that the dissociated OH from H2O on BaO reacts with C on Ni near the BaO/Ni interface to produce CO and H species, which are then electrochemically oxidized at the triple-phase boundaries of the anode. This anode offers potential for ushering in a new generation of SOFCs for efficient, low-emission conversion of readily available fuels to electricity.

Rational SOFC material design: new advances and tools

Solid oxide fuel cells (SOFCs) offer great prospects for the most efficient and cost-effective utilization of a wide variety of fuels. However, their commercialization hinges on the rational design of low cost materials with exceptional functionalities. This article highlights some recent progress in probing and mapping surface species and incipient phases relevant to electrode reactions using in situ Raman spectroscopy, synchrotron based x-ray analysis, and multi-scale modeling of charge and mass transport. The combination of in situ characterization and multi-scale modeling is imperative to unraveling the mechanisms of chemical and energy transformation: a vital step for the rational design of next generation SOFC materials.

Enhancement of La0.6Sr0.4Co0.2Fe0.8O3-δ durability and surface electrocatalytic activity by La0.85Sr0.15MnO3±δ investigated using a new test electrode platform

A carefully designed test cell platform with a new electrode structure is utilized to determine the intrinsic surface catalytic properties of an electrode. With this design, the electrocatalytic activity and stability of an La0.6Sr0.4Co0.2Fe0.8O3−δ (LSCF) cathode is enhanced by a dense thin La0.85Sr0.15MnO3±δ (LSM) coating, suggesting that an efficient electrode architecture has been demonstrated that can make effective use of desirable properties of two different materials: fast ionic and electronic transport in the backbone (LSCF) and facile surface kinetics on the thin-film coating (LSM). Theoretical analyses suggest that the enhanced electrocatalytic activity of LSM-coated LSCF is attributed possibly to surface activation under cathodic polarization due to the promotion of oxygen adsorption and/or dissociation by the surface layer and the dramatically increased oxygen vacancy population in the surface film. Further, the observed time-dependent activation over a few hundreds of hours and durability are likely associated with the formation of a favorable hybrid surface phase intermediate between LSM and LSCF. This efficient electrode architecture was successfully applied to the state-of-the-art LSCF-based cathodes by a simple solution infiltration process, achieving reduced interfacial resistance and improved stability under fuel cell operating conditions.

Raman spectroscopic monitoring of carbon deposition on hydrocarbon-fed solid oxide fuel cell anodes

Solid oxide fuel cells (SOFCs) are potentially the most efficient and cost-effective solution for the utilization of a wide variety of fuels beyond hydrogen. One of the chief obstacles to true fuel flexibility lies in anode deactivation by coking as well as a limited mechanistic understanding of coking and its prevention. Here we report Raman spectroscopic mapping and monitoring of carbon deposition on SOFC anode surfaces under both ex situ and in situ conditions. Carbon mapping was successfully demonstrated with a model Ni–YSZ electrode exposed to a CH4-containing atmosphere at high temperature (625 °C), while carbon deposition over time in a wet C3H8 atmosphere was directly monitored on a similar anode system as well as a BaO-modified system. This spectroscopic technique provides valuable insight into the mechanism of carbon deposition, which is vital in achieving rational design of carbon-tolerant anode materials.

High-temperature surface enhanced Raman spectroscopy for in situ study of solid oxide fuel cell materials

In situ probing of surface species and incipient phases is vital to unraveling the mechanisms of chemical and energy transformation processes. Here we report Ag nanoparticles coated with a thin-film SiO2 shell that demonstrate excellent thermal robustness and chemical stability for surface enhanced Raman spectroscopy (SERS) study of solid oxide fuel cell materials under in situ conditions (at ∼400 °C).

Application of surface enhanced Raman spectroscopy to the study of SOFC electrode surfaces

SERS provided by sputtered silver was employed to detect trace amounts of chemical species on SOFC electrodes. Considerable enhancement of Raman signal and lowered detection threshold were shown for coked nickel surfaces, CeO(2) coatings, and cathode materials (LSM and LSCF), suggesting a viable approach to probing electrode degradation and surface catalytic mechanism.

Strong coupling between Rhodamine 6G and localized surface plasmon resonance of immobile Ag nanoclusters fabricated by direct current sputtering

We made clean silver nano-clusters (AgNCs) on glass substrates by DC magnetron sputtering of a high purity Ag target in a high vacuum chamber. The AgNCs film shows strong localized surface plasmon resonance (LSPR) due to the coupling among Ag nanoparticles in the AgNCs and the coupling between AgNCs. The LSPR indicates strong coupling with Rhodamine 6G (R6G) adsorbed on the AgNC surface, which enhances the R6G absorption intensity and broadens the absorption wavelength range. This result promotes plasmonic nanoparticles to be better used in solar cells.

Electrostatic Force Microscopic Characterization of Early Stage Carbon Deposition on Nickel Anodes in Solid Oxide Fuel Cells

Carbon deposition on nickel anodes degrades the performance of solid oxide fuel cells that utilize hydrocarbon fuels. Nickel anodes with BaO nanoclusters deposited on the surface exhibit improved performance by delaying carbon deposition (i.e., coking). The goal of this research was to visualize early stage deposition of carbon on nickel surface and to identify the role BaO nanoclusters play in coking resistance. Electrostatic force microscopy was employed to spatially map carbon deposition on nickel foils patterned with BaO nanoclusters. Image analysis reveals that upon propane exposure initial carbon deposition occurs on the Ni surface at a distance from the BaO features. With continued exposure, carbon deposits penetrate into the BaO-modified regions. After extended exposure, carbon accumulates on and covers BaO. The morphology and spatial distribution of deposited carbon was found to be sensitive to experimental conditions.

Resonant surface enhancement of Raman scattering of Ag nanoparticles on silicon substrates fabricated by dc sputtering

Ag nanoparticles (AgNPs) were deposited onto silicon substrates by direct current (dc) magnetron sputtering. The influences of sputtering power and sputtering time on the AgNP film morphology were studied using atomic force microscopy. The particle size was successfully tuned from 19 nm to 53 nm by varying the sputtering time at a dc power of 10 W. When Rhodamine 6 G (R6G) was used as the probe molecule, the AgNP films showed significant surface enhanced Raman scattering effect. In particular, it is found that larger particles show stronger enhancement for lower concentrations of R6G while smaller particles display stronger enhancement for higher concentrations of R6G.