Jihwan An

Three-Dimensional Nanostructured Bilayer Solid Oxide Fuel Cell with 1.3 W/cm 2 at 450 °C

Obtaining high power density at low operating temperatures has been an ongoing challenge in solid oxide fuel cells (SOFC), which are efficient engines to generate electrical energy from fuels. Here we report successful demonstration of a thin-film three-dimensional (3-D) SOFC architecture achieving a peak power density of 1.3 W/cm(2) obtained at 450 °C. This is made possible by nanostructuring of the ultrathin (60 nm) electrolyte interposed with a nanogranular catalytic interlayer at the cathode/electrolyte interface. We attribute the superior cell performance to significant reduction in both the ohmic and the polarization losses due to the combined effects of employing an ultrathin film electrolyte, enhancement of effective area by 3-D architecture, and superior catalytic activity by the ceria-based interlayer at the cathode. These insights will help design high-efficiency SOFCs that operate at low temperatures with power densities that are of practical significance.

Atomic Scale Verification of Oxide-Ion Vacancy Distribution near a Single Grain Boundary in YSZ

This study presents atomic scale characterization of grain boundary defect structure in a functional oxide with implications for a wide range of electrochemical and electronic behavior. Indeed, grain boundary engineering can alter transport and kinetic properties by several orders of magnitude. Here we report experimental observation and determination of oxide-ion vacancy concentration near the Σ13 (510)/[001] symmetric tilt grain-boundary of YSZ bicrystal using aberration-corrected TEM operated under negative spherical aberration coefficient imaging condition. We show significant oxygen deficiency due to segregation of oxide-ion vacancies near the grain-boundary core with half-width < 0.6 nm. Electron energy loss spectroscopy measurements with scanning TEM indicated increased oxide-ion vacancy concentration at the grain boundary core. Oxide-ion density distribution near a grain boundary simulated by molecular dynamics corroborated well with experimental results. Such column-by-column quantification of defect concentration in functional materials can provide new insights that may lead to engineered grain boundaries designed for specific functionalities.

Plasma processing for crystallization and densification of atomic layer deposition BaTiO3 thin films.

High-k, low leakage thin films are crucial components for dynamic random access memory (DRAM) capacitors with high storage density and a long storage lifetime. In this work, we demonstrate a method to increase the dielectric constant and decrease the leakage current density of atomic layer deposited BaTiO3 thin films at low process temperature (250 °C) using postdeposition remote oxygen plasma treatment. The dielectric constant increased from 51 (as-deposited) to 122 (plasma-treated), and the leakage current density decreased by 1 order of magnitude. We ascribe such improvements to the crystallization and densification of the film induced by high-energy ion bombardments on the film surface during the plasma treatment. Plasma-induced crystallization presented in this work may have an immediate impact on fabricating and manufacturing DRAM capacitors due to its simplicity and compatibility with industrial standard thin film processes.

Nanotubular array solid oxide fuel cell.

This report presents a demonstration and characterization of a nanotubular array of solid oxide fuel cells (SOFCs) made of one-end-closed hollow tube Ni/yttria-stabilized zirconia/Pt membrane electrode assemblies (MEAs). The tubular MEAs are nominally ∼5 μm long and have <500 nm outside diameter with total MEA thickness of nearly 50 nm. Open circuit voltages up to 660 mV (vs air) and power densities up to 1.3 μW cm(-2) were measured at 550 °C using H2 as fuel. The paper also introduces a fabrication methodology primarily based on a template process involving atomic layer deposition and electrodeposition for building the nanotubular MEA architecture as an important step toward achieving high surface area ultrathin SOFCs operating in the intermediate to low-temperature regime. A fabricated nanotubular SOFC theoretically attains a 20-fold increase in the effective surface, while projections indicate the possibility of achieving up to 40-fold.

Aberration-Corrected TEM Imaging of Oxygen Occupancy in YSZ

We present atomic-scale imaging of oxygen columns and show quantitative analysis on the occupancy of the columns in yttria-stabilized zirconia (YSZ) using aberration-corrected TEM operated under the negative Cs condition. Also, individual contributions both from oxygen column occupancy and the static displacement of oxygen atoms due to occupancy change to the observed column intensities of TEM images were systematically investigated using HRTEM simulation. We found that oxygen column intensity is governed primarily by column occupancy rather than by static displacement of oxygen atoms. Utilizing the aberration-corrected TEM capability and HRTEM simulation results, we experimentally verified that oxygen vacancies segregate near the single grain boundary of a YSZ bicrystal. The methodology and the high spatial resolution characterization tool employed in the present study provide insights into the distribution of oxygen vacancies in the bulk as well as near grain boundaries and pave the way for further investigation and atomic-scale analysis in other important oxide materials.

Enhancing Charge Transfer Kinetics by Nanoscale Catalytic Cermet Interlayer

Enhancing the density of catalytic sites is crucial for improving the performance of energy conversion devices. This work demonstrates the kinetic role of 2 nm thin YSZ/Pt cermet layers on enhancing the oxygen reduction kinetics for low temperature solid oxide fuel cells. Cermet layers were deposited between the porous Pt cathode and the dense YSZ electrolyte wafer using atomic layer deposition (ALD). Not only the catalytic role of the cermet layer itself but the mixing effect in the cermet was explored. For cells with unmixed and fully mixed cermet interlayers, the maximum power density was enhanced by a factor of 1.5 and 1.8 at 400 °C, and by 2.3 and 2.7 at 450 °C, respectively, when compared to control cells with no cermet interlayer. The observed enhancement in cell performance is believed to be due to the increased triple phase boundary (TPB) density in the cermet interlayer. We also believe that the sustained kinetics for the fully mixed cermet layer sample stems from better thermal stability of Pt islands separated by the ALD YSZ matrix, which helped to maintain the high-density TPBs even at elevated temperature.

Fluorine contamination in yttrium-doped barium zirconate film deposited by atomic layer deposition

The authors have investigated the change of chemical composition, crystallinity, and ionic conductivity in fluorine contaminated yttrium-doped barium zirconate (BYZ) fabricated by atomic layer deposition (ALD). It has been identified that fluorine contamination can significantly affect the conductivity of the ALD BYZ. The authors have also successfully established the relationship between process temperature and contamination and the source of fluorine contamination, which was the perfluoroelastomer O-ring used for vacuum sealing. The total removal of fluorine contamination was achieved by using all-metal sealed chamber instead of O-ring seals.

Atomic layer deposition of ultrathin blocking layer for low-temperature solid oxide fuel cell on nanoporous substrate

An ultrathin yttria-stabilized zirconia (YSZ) blocking layer deposited by atomic layer deposition (ALD) was utilized for improving the performance and reliability of low-temperature solid oxide fuel cells (SOFCs) supported by an anodic aluminum oxide substrate. Physical vapor-deposited YSZ and gadolinia-doped ceria (GDC) electrolyte layers were deposited by a sputtering method. The ultrathin ALD YSZ blocking layer was inserted between the YSZ and GDC sputtered layers. To investigate the effects of an inserted ultrathin ALD blocking layer, SOFCs with and without an ultrathin ALD blocking layer were electrochemically characterized. The open circuit voltage (1.14 V) of the ALD blocking-layered SOFC was visibly higher than that (1.05 V) of the other cell. Furthermore, the ALD blocking layer augmented the power density and improved the reproducibility.

Properties of nanostructured undoped ZrO2 thin film electrolytes by plasma enhanced atomic layer deposition for thin film solid oxide fuel cells

Nanostructured ZrO2 thin films were prepared by thermal atomic layer deposition (ALD) and by plasma-enhanced atomic layer deposition (PEALD). The effects of the deposition conditions of temperature, reactant, plasma power, and duration upon the physical and chemical properties of ZrO2 films were investigated. The ZrO2 films by PEALD were polycrystalline and had low contamination, rough surfaces, and relatively large grains. Increasing the plasma power and duration led to a clear polycrystalline structure with relatively large grains due to the additional energy imparted by the plasma. After characterization, the films were incorporated as electrolytes in thin film solid oxide fuel cells, and the performance was measured at 500 °C. Despite similar structure and cathode morphology of the cells studied, the thin film solid oxide fuel cell with the ZrO2 thin film electrolyte by the thermal ALD at 250 °C exhibited the highest power density (38 mW/cm2) because of the lowest average grain size at cathode/electro...

Surface engineering of nanoporous substrate for solid oxide fuel cells with atomic layer-deposited electrolyte

Summary Solid oxide fuel cells with atomic layer-deposited thin film electrolytes supported on anodic aluminum oxide (AAO) are electrochemically characterized with varying thickness of bottom electrode catalyst (BEC); BECs which are 0.5 and 4 times thicker than the size of AAO pores are tested. The thicker BEC ensures far more active mass transport on the BEC side and resultantly the thicker BEC cell generates ≈11 times higher peak power density than the thinner BEC cell at 500 °C.