Enhancing Active Surface Area and Gas Diffusion Properties of Low-Temperature Solid Oxide Fuel Cell Cathodes by Sputtering with Glancing Angle Deposition.

Solid oxide fuel cells (SOFCs) attract attentions as high-efficiency energy-conversion devices. In order to establish high-performance SOFCs, the slow electrode kinetics, which is often a main cause of the energy loss, should be improved. In present SOFCs, mixed ionic-electronic conducting (MIEC) oxides, such as (La,Sr)CoO3 -δ and (La,Sr)(Co,Fe)O3 -δ , are typically used as the cathode materials. In such an MIEC cathode, it is generally believed that electrochemical oxygen reduction reaction takes place mainly at the oxide surfaces (double phase boundary, DPB) and the contribution of the reaction at the electrode/electrolyte/gas interface (triple phase boundary, TPB) is insignificant. Therefore, researches on the kinetics of SOFC cathodic reaction have mostly concerned to investigate the surface reaction on the electrode oxides. In our previous works, the reaction distributions in MIEC SOFC electrodes were experimentally evaluated by using operando micro X-ray absorption spectroscopy (operando μ-XAS) [1, 2]. For more quantitative and precise investigation of the reaction distribution, we proposed a patterned thin film electrode, which is a kind of the columnar electrode simplifying the microstructures of a porous electrode [2]. However, the patterned thin film electrode in our previous work did not have triple phase boundaries, and it was thus impossible to discuss the contribution of TPB reaction to the total reaction. In this work, a patterned thin film electrode having triple phase boundaries was fabricated. (La,Sr)CoO3- d (LSC) was chosen as the model MIEC oxide for SOFC cathodes. The reaction distribution in this new type of the patterned thin film electrode was experimentally determined by using operando μ-XAS, and the results were compared with ones obtained with the old type of the patterned thin film electrode without TPB. It was found the effective reaction area tended to shrink by the introduction of TPB to the patterned thin film electrode. This fact might suggest that the reaction at TPBs in SOFC cathodes is not negligible even when MIEC oxides are used as electrode materials.

Solid Oxide Fuel Cells (SOFCs) are energy conversion devices known for their significantly higher power density compared to other fuel cell types. However, their high operating temperatures pose challenges related to thermal stability. To address this, research is focusing on Low-Temperature SOFCs (LT-SOFCs), which function at lower temperatures and exhibit enhanced electrochemical performance. While various electrode materials are utilized in SOFCs, platinum (Pt) stands out for its excellent electronic conductivity and catalytic activity. Unfortunately, at the operating temperatures of SOFCs, Pt tends to agglomerate, leading to a rapid reduction in the triple phase boundary (TPB) and a subsequent decline in electrochemical reactions. In this study, LT-SOFCs were fabricated with a Praseodymium Oxide (PrOx) capping layer applied to a porous Pt cathode using sputtering, with various thicknesses achieved by adjusting the deposition time. The electrochemical performance of the LT-SOFCs was measured at 500oC. Additionally, the degradation behavior of the LT-SOFCs was assessed by applying a constant voltage of 0.5 V for 48 hours. Scanning Electron Microscopy (SEM) analysis was also conducted on the PrOx capping layer thin films under the same operating conditions.

A gadolinia-doped ceria (GDC) capping layer was fabricated on a metal Pt cathode via a sputtering technique to enhance the thermal stability and oxygen-reduction reaction (ORR) kinetics. By varying the thickness of the GDC thin film on the Pt cathode, we fabricated thermally durable low-temperature solid oxide fuel cells (LT-SOFCs) on porous anodized aluminum oxide (AAO) substrates while securing very high performance. The GDC protective layers subsequently mitigated the agglomeration of the Pt morphology by hindering the coarsening of metal grains, and enhanced the cathodic kinetics as a result of the increased TPB density at the Pt-electrolyte interface. Enhanced performance of fuel cells and thermo-stable behavior with the GDC capping layer were demonstrated by employing transmission electron microscopy (TEM) and electrochemical analysis. An enhanced peak power density of 258 mW/cm2 was obtained with a degradation of 56.4% of the Pt cathode over 25 hours of operation at 450°C.

This study demonstrated a silver (Ag) and samarium-doped ceria (SDC) mixed ceramic and metal composite (i.e., cermet) as a cathode for low-temperature solid oxide fuel cells (LT-SOFCs). Introducing the Ag-SDC cermet cathode for LT-SOFCs revealed that the ratio between Ag and SDC, which is a crucial factor for catalytic reactions, can be tuned by the co-sputtering process, resulting in enhanced triple phase boundary (TPB) density in the nanostructure. Ag-SDC cermet not only successfully performed as a cathode to increase the performance of LT-SOFCs by decreasing polarization resistance but also exceeded the catalytic activity of platinum (Pt) due to the improved oxygen reduction reaction (ORR). It was also found that less than half of Ag content was effective to increase TPB density, preventing oxidation of the Ag surface as well.

La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) symmetric-electrode cells with Gd0.1Ce0.9O1.95 (GDC) electrolytes were aged in ambient air at temperatures ranging from 550 to 950°C for times up to 1400 h, without current/polarization. Electrochemical impedance spectroscopy measurements, taken periodically during the tests at a testing temperature of 700°C for cells aged at 700, 750 and 800°C, showed a continuous increase in polarization resistance. Focused ion beam-scanning electron microscopy (FIB-SEM) 3D tomography showed that the LSCF electrode did not coarsen measurably at ageing temperatures ≤ 800°C, ruling out LSCF microstructural changes as the mechanism behind the resistance increase. On the other hand, Sr surface segregation, determined by chemical etching with inductively coupled plasma-optical emission spectrometry (ICP-OES) detection, was found to increase with increasing ageing time and temperature > 650°C. The effect of Sr surface segregation on the oxygen surface exchange and diffusion processes is quantified by comparing the measured electrochemical and microstructural data.

Pulverization characteristics of coal from a strong outburst-prone coal seam and their impact on gas desorption and diffusion properties

YSZ ( yttria-stabilized zirconia)-modified LSM composite cathodes were fabricated by formation of YSZ film on triple phase boundary (TPB) of LSM/YSZ/gas. The YSZ coating film greatly enlarged electrochemical reaction sites from the increase of additional TPB. The composite cathode was formed on thin YSZ electrolyte (about 30 Um thickness) supported on an anode and then I-V characterization and AC impedance analyses were performed at temperature between . As results of the impedance analysis on the cell at with humidified hydrogen as the fuel and air as the oxidant, R1 around the frequency of 1000 Hz represents the anode Polarization. R2 around the frequency of 100Hz indicates the cathode polarization, and R3 below the frequency of 10 Hz is the resistance of gas phase diffusion through the anode. The cell with the composite cathode produced power density of at air and oxygen atmosphere, respectively. The I-V curve could be divided into two parts showing distinctive behavior. At low current density region (part I) the performance decreased steeply and at high current density region (part II) the performance decreased gradually. At the part I the performance decrease was especially resulted from the large cathode polarization, while at the part H the performance decrease related to the electrolyte polarization.

The performance of solid oxide fuel cell cathodes can be improved by increasing the number of electrochemical reaction sites. This is often done by controlling microstructures and using composite materials that consist of an ionic conductor and a mixed ionic and electronic conductor. LSCF (La0.6Sr0.4Co0.2Fe0.8O3-δ) and SSC (Sm0.5Sr0.5CoO3) cathodes were manufactured by axial-injection atmospheric plasma spraying (APS), and composite cathodes were fabricated by mixing SDC (Ce0.8Sm0.2O1.9) into the feedstock powders. The plasma power was varied by changing the proportion of nitrogen in the plasma gas. The microstructures of cathodes produced with different plasma powers were characterized by scanning electron microscopy and gas permeation measurements. The deposition efficiencies of these cathodes were calculated based on the mass of the sprayed cathode. Particle surface temperatures were measured in-flight to enhance understanding of the relationship between spray parameters, microstructure, and deposition efficiency.

The classic challenge faced by researchers dealing with liquid crystals is to control the LC molecular orientation and hence optimise the optical properties. Well known techniques for influencing LC texture include the use of surfactants or thin film alignment layers. The underlying limitation common to such techniques is that while excellent control of LC anchoring at the substrate surface is achieved, molecular alignment in the bulk of the LC is reliant entirely upon the cooperative effects and resulting elastic properties of the LC material. Generally, this has worked sufficiently well in practice, but unfortunately, the complete dependence on the intermolecular forces of the LC means that unencumbered, reversible switching is not always possible. Our group has taken a unique approach to influence LC orientation. Using glancing angle deposition (GLAD), highly porous thin films can be grown possessing isolated columnar microstructure whose shape can be tailored via substrate motion during film deposition. In particular, we can grow films of helical columns with controlled pitch and handedness. These films exhibit circular dichroism and optical activity similar to that seen in chiral LCs. The high porosity of GLAD films permits fluids such as LCs to be introduced into the pores, leading to a new type of hybrid optical material. Most significantly, initial work showed that when achiral LCs were embedded in chiral GLAD media, there was an enhancement of the circular dichroism and optical activity as the chiral GLAD film served to induce a chiral orientation in the LC. In this report, we start with a brief overview of the GLAD process and some relevant optical studies, leading to a review of GLAD/LC hybrid materials, switchable devices, and finally, a discussion of recent research optical characterisation and some ideas for future avenues of investigation.

Fast oxygen reduction reaction (ORR) at the cathode is a key requirement for the realization of low-temperature solid oxide fuel cells (SOFCs). While the design of three-dimensional (3D) structures has emerged as a new and promising approach to improving the electrochemical performance of SOFC cathodes, achieving versatile structures and structural stability is still challenging. In this study, we demonstrate a novel architectural design for a superior cathode with fast ORR activity. By employing a completely new fabrication process comprising a 3D printing technique and pulsed laser deposition (PLD), we design 3D La0.8Sr0.2CoO3-δ (LSC) micro-nano structures with the desired shape. 3D-printed yttria-stabilized ZrO2 (YSZ) microstructures significantly increase the ratio of surface area to volume while maintaining suitable ionic conductivity comparable to that of single-crystalline YSZ substrates. Scanning electron microscopy and energy dispersive X-ray microanalysis reveal the formation of crack- or void-free YSZ microstructures and the uniform deposition of LSC films by PLD on the YSZ microstructures. The 3D LSC micro-nano structures show significantly enhanced oxygen surface exchange coefficients (kchem) extracted from electrical conductivity relaxation (ECR) measurements by up to 3 orders of magnitude relative to the bulk LSC. Furthermore, electrochemical impedance spectroscopy measurements verify the kchem values from ECR and no directional difference in the measured ORR activity depending on the shape of 3D microstructures. The dramatic enhancement of the ORR activity of LSC is attributed to the increased film surface areas resulting from the 3D YSZ microstructures.

The comprehensive research plan for Fuel Cells focused on Solid State Energy Conversion Alliance (SECA) programmatic targets and included objectives in two primary and focused areas: (1) investigation of degradation modes exhibited by the anode/electrolyte/cathode (AEC), development of computational models describing the associated degradation rates, and generation of a modeling tool predicting long term AEC degradation response; and (2) generation of novel electrode materials and microstructures and implementation of the improved electrode technology to enhance performance. In these areas, the National Energy Technology Laboratory (NETL) Regional University Alliance (RUA) team has completed and reported research that is significant to the SECA program, and SECA continued to engage all SECA core and SECA industry teams. Examination of degradation in an operational solid oxide fuel cell (SOFC) requires a logical organization of research effort into activities such as fundamental data gathering, tool development, theoretical framework construction, computational modeling, and experimental data collection and validation. Discrete research activity in each of these categories was completed throughout the year and documented in quarterly reports, and researchers established a framework to assemble component research activities into a single operational modeling tool. The modeling framework describes a scheme for categorizing the component processes affecting the temporal evolution of cell performance, and provides a taxonomical structure of known degradation processes. The framework is an organizational tool that can be populated by existing studies, new research completed in conjunction with SECA, or independently obtained. The Fuel Cell Team also leveraged multiple tools to create cell performance and degradation predictions that illustrate the combined utility of the discrete modeling activity. Researchers first generated 800 continuous hours of SOFC experimental data capturing operational degradation. The data were matched by a 3D multi-physics simulation of SOFC operational performance assuming that the entire performance loss related to coarsening of the cathode triple phase boundary (3PB). The predicted 3PB coarsening was then used to tune the mobility parameters of a phase field model describing microstructural evolution of the lanthanum strontium manganate (LSM)/ yttria stabilized zirconia (YSZ) system. Once calibrated, the phase field model predicted continuous microstructural coarsening processes occurring over the operating period, which could be extrapolated to performance periods of longer duration and also used to produce 3D graphical representations. NETL researchers also completed significant electrode engineering research complimented by 3D multi-physics simulations. In one key activity researchers generated an illustration demonstrating that control of infiltrate deposition can provide cell manufacturers with significant additional operational and engineering control over the SOFC stack. Specifically, researchers demonstrated that by engineering the deposition of electrocatalyst inside the cathode, the distribution of overpotential across the cell could be controlled to either decrease the average cell overpotential value or minimize cross-cell overpotential gradient. Results imply that manufacturers can establish improved engineering control over stack operation by implementing infiltration technology in SOFC cathodes.

ABSTRACTWe report a process for the successful incorporation of ceria in to yttria-stabilized zirconia (YSZ) columnar nanostructures grown by glancing angle deposition (GLAD) technique, resulting in high interface density columnar nanostructures. The incorporation of ceria into YSZ columns is confirmed by scanning electron microscopy (SEM) in a cross sectional geometry with in-situ analysis of elemental x-ray mapping technique and energy dispersive x-ray analysis (EDX). Controlled engineering of such nanostructures is potentially important in the future development of high efficiency solid oxide fuel cell electrolytes. The challenges and advantages of this process are discussed.

A high performance solid oxide fuel cell cathode using the yttria-stabilized zirconia (YSZ) nanofiber scaffold with the infiltrated La1−xSrxMnO3 (LSM) shows an enhanced catalytic activity toward oxygen reduction. Such a cathode offers a continuous path for charge transport and an increased number of triple-phase boundary sites.

Solid oxide fuel cells (SOFCs) are getting more importance with their promising future, due to their high-energy conversion efficiency, low-emissions and flexibility of usable fuel type. The performance and the lifetime of SOFCs are keenly dependent on electrode microstructure. In order to recognize the microstructural evolution and its degradation kinetics in SOFC cermet cathodes during long exposure time (up to 20 000 h) under realistic operating conditions ( T= 850 °C, J= 190-250 ), investigations on porous LSM/YSZ cathodes were conducted. The 3D-tomography technique (FIB/SEM) offers extensive data about the microstructures of various cathode aged during different operating times (2 500 h, 15 000 h and 20 000 h), which allows an exact quantification of particle size distribution, phase-connectivity, tortuosity factor and Triple Phase Boundary Length (TPBL). With the increasing operating time no significant 3D microstructural changes in the cathode were noticed in the obtained data. However, additional qualitative X-ray fluorescence measurement, indicate a clear presence of chrome contamination on aged cathodes, which may be the main degradation mechanism in the SOFC cathode. Keywords: chrome poisoning, long operating time, particle size distribution, SOFC, triple phase boundary, SEM, XRF

Effect of calcination temperature on sensing performance of YSZ based electrochemical H2S gas sensor with a NiFe2O4 electrode