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Ni-YSZ electrode support symmetric cells were operated at 0, 0.75, 1.00, and 1.50 A/cm 2 for 1000 h in 50% H 2 -50% H 2 O at 800 ˚C. Electrochemical fracture at the anode-electrolyte interface is observed to occur under high anodic overpotential. Ni migration is observed and quantified over time at the anode of the polarized cells; however, the cathode shows no migration compared to control. Gas diffusion calculations show that steam is significantly enriched and depleted at the anode and cathode respectively, leading to the formation or suppression of volatile Ni(OH) x species, which have been hypothesized as a transport pathway for Ni. However; gas flux calculations show that chemical evaporation alone is unlikely to be fast enough to induce the Ni loss observed. 

In Ni-YSZ electrode-supported cells, gas diffusion through the electrode support layer can be a significant limitation at high H 2 or H 2 O utilization and high temperature. Conventionally, higher-porosity electrode supports are used to improve diffusion, but this diminishes the cell’s structural integrity. Alternative fabrication methods like freeze-casting and 3D-printing allow for the creation of hierarchical structures with cutouts in the cell surface that improve gas diffusion, but these methods require redesigning processing procedures to obtain the desired materials properties. This work explores the use of laser ablation to pattern cutouts into the electrode support after sintering, enabling a faster mass transport without redesigning the entire fabrication process. Current-voltage measurements of symmetric Ni-YSZ electrode-supported cells with one patterned and one un-patterned electrode demonstrate that laser-patterning improves limiting current density and effective diffusivity by as much as 30%. Mechanical testing of patterned and un-patterned cells demonstrates that patterned cells suffer relatively small reductions in fracture strength. 

Solid oxide cell long-term durability experiments are resource-intensive and have limited ability to capture the interdependence of microstructural evolution and electrochemical performance. Studies of microstructural degradation mechanisms are usually limited to before and after life-test images. Here we describe a life testing method that simultaneously operates multiple symmetric cells under different conditions, simultaneously providing information on electrolysis and fuel cell operation, while sampling the microstructure during operation. The method utilizes laser-cutting to exactly define different cell areas, allowing testing under different current densities with a single current source, and facilitating removal of segments of the cellsduringlife tests, allowing for microstructural evaluation at intermediate times. The method is demonstrated in Ni-YSZ / YSZ / Ni-YSZ fuel-electrode-supported cells at low H₂O/H₂ratios. Characterization using SEM-based imaging techniques shows pronounced microstructural damage that increases rapidly with increasing current density and time, mirroring observed electrochemical degradation. The present results agree with prior reports for SOC operation under such conditions but reveal new features of the degradation process via the unique capability of time-resolved imaging. 

Electrochemical impedance spectroscopy (EIS) is a powerful technique for material characterization and diagnosis of the solid oxide fuel cells (SOFC) as it enables separation of different phenomena such as bulk diffusion and surface reaction that occur simultaneously in the SOFC. In this work, we simulate the electrochemical impedance in an experimentally determined, three-dimensional (3D) microstructure of a mixed ion-electron conducting (MIEC) SOFC cathode. We determine the impedance response by solving the mass conservation equation in the cathode under the conditions of an AC load across the cathode’s thickness and surface reaction at the pore/solid interface. Our simulation results reveal a need for modifying the Adler-Lane-Steele model, which is widely used for fitting the impedance behavior of a MIEC cathode, to account for the difference in the oscillation amplitudes of the oxygen vacancy concentration at the pore/solid interface and within the solid bulk. Moreover, our results demonstrate that the effective tortuosity is dependent on the frequency of the applied AC load as well as the material properties, and thus the prevalent practice of treating tortuosity as a constant for a given cathode should be revised. Finally, we propose a method of determining the aforementioned dependence of tortuosity on material properties and frequency by using the EIS data. 

The dataset associated with the article: Goel, V., Cox, D., Barnett, S. A., & Thornton, K. (2021). Simulation of the electrochemical impedance in a three-dimensional, complex microstructure of solid oxide fuel cell cathode and its application in the microstructure characterization. Frontiers in Chemistry, 9, 627699. 

This paper addresses the use of Ce 0.8 Gd 0.2 O 2−δ (GDC) infiltration into the Ni–(Y 2 O 3 ) 0.08 (ZrO 2 ) 0.92 (YSZ) fuel electrode of solid oxide cells (SOCs) for improving their electrochemical performance in fuel cell and electrolysis operation. Although doped ceria infiltration into Ni–YSZ has recently been shown to improve the electrode performance and stability, the mechanisms defining how GDC impacts electrochemical characteristics are not fully delineated. Furthermore, the electrochemical characteristics have not yet been determined over the full range of conditions normally encountered in fuel cell and electrolysis operation. Here we present a study of both symmetric and full cells aimed at understanding the electrochemical mechanisms of GDC-modified Ni–YSZ over a wide range of fuel compositions and temperatures. Single-step GDC infiltration at an appropriate loading substantially reduced the polarization resistance of Ni–YSZ electrodes in electrolyte-supported cells, as measured using electrochemical impedance spectroscopy (EIS) at various temperatures (600–800 °C) in a range of H 2 O–H 2 mixtures (3–90 vol% H 2 O). Fuel-electrode-supported cells had significant concentration polarization due to the thick Ni–YSZ supports. A distribution of relaxation times approach is used to develop a physically-based electrochemical model; the results show that GDC reduces the reaction resistance associated with three-phase boundaries, but also appears to improve oxygen transport in the electrode. Increasing the H 2 O fraction in the H 2 –H 2 O fuel mixture reduced both the three-phase boundary resistance and the gas diffusion resistance for Ni–YSZ; with GDC infiltration, the electrode resistance showed less variation with fuel composition. GDC infiltration improved the performance of fuel-electrode-supported full cells, which yielded a maximum power density of 2.28 W cm −2 in fuel cell mode and an electrolysis current density at 1.3 V of 2.22 A cm −2 , both at 800 °C. 

Solid oxide cells (SOCs) have important applications as fuel cells and electrolyzers. The application for storage of renewable electricity is also becoming increasingly relevant; however, it is difficult to meet stringent area-specific resistance (ASR) and long-term stability targets needed to achieve required efficiency and cost. Here we show a new SOC that utilizes a very thin Gd-doped ceria (GDC)/yttria-stabilized zirconia (YSZ) bi-layer electrolyte, Ni–YSZ cell support with enhanced porosity, and electrode surface modification using PrO x and GDC nanocatalysts to achieve unprecedented low ASR values < 0.1 Ω cm 2 , fuel cell power density ∼3 W cm −2 , and electrolysis current density ∼4 A cm −2 at 800 °C. Besides this exceptionally high performance, fuel cell and electrolysis life tests suggest very promising stability in fuel cell and steam electrolysis modes. Electrochemical impedance spectroscopy analysis done using a novel impedance subtraction method shows how rate-limiting electrode processes are impacted by the new SOC materials and design. 

Sr(Ti 1−x Fe x )O 3−δ (STF) has recently been explored as an oxygen electrode for solid oxide electrochemical cells (SOCs). Model thin film electrode studies show oxygen surface exchange rates that generally improve with increasing Fe content when x < 0.5, and are comparable to the best Co-containing perovskite electrode materials. Recent results on porous electrodes with the specific composition Sr(Ti 0.3 Fe 0.7 )O 3−δ show excellent electrode performance and stability, but other compositions have not been tested. Here we report results for porous electrodes with a range of compositions from x = 0.5 to 0.9. The polarization resistance decreases with increasing Fe content up to x = 0.7, but increases for further increases in x . This results from the interaction of two effects – the oxygen solid state diffusion coefficient increases with increasing x , but the electrode surface area and surface oxygen exchange rate decrease due to increased sinterability and Sr surface segregation for the Fe-rich compositions. Symmetric cells showed no degradation during 1000 h life tests at 700 °C even at a current density of 1.5 A cm −2 , showing that all the STF electrode compositions worked stably in both fuel cell mode and electrolysis modes. The excellent stability may be explained by X-ray Photoelectron Spectroscopy (XPS) results showing that the amount of surface segregated Sr did not change during the long-term testing, and by relatively low polarization resistances that help avoid electrode delamination.