Time-Resolved Characterization of Electrochemically-Induced Solid Oxide Cell Microstructure Evolution
Authors: Cox Dalton , Barnett Scott A 
Published: July 2022

Solid oxide cells (SOC) are exciting both for their capability of fuel-flexible electricity generation and their promise in the production of green H2; however, their degradation and long-term performance remain important questions. Operating individual button cells to characterize these changes is prone to cell-to-cell variations, whereas large-area cell/stack life testing requires considerable resources. In both cases, full cell characterization usually must wait until the completion of the life test, which may delay getting results for months or years. While progress has been made in observing microstructural changes over time (termed here time-resolved characterization) using techniques like non-destructive transmission x-ray microscope tomography, such experiments are difficult to implement, especially the effect of current is unexplored due to geometrical and gas environmental limitations of the system.
Presented here is a method to rapidly obtain time-resolved microstructural information of the same cell in tandem with electrochemical measurements. While SOC degradation arises due to a range of processes, this work focuses on the microstructural evolution of Ni-YSZ fuel electrodes that occurs during electrolysis operation, which is known to be a key issue. Two key experimental features allowed time-resolved characterization of multiple cells simultaneously: (1) the use of Ni-YSZ symmetric cells allows multiple cells of different size in a single test by avoiding the need for gas seals, and (2) the use of laser milling to allow controlled removal of a portion of each cell during the test.
Here we illustrate the method for the case of low steam content and high current density, designed to exacerbate and accelerate electrolysis degradation due to the highly reducing conditions achieved. Tape-cast planar electrode-supported Ni-YSZ symmetric cells were laser cut into precise geometries with well-defined projected areas and easily removable sections. Four cells with projected areas of 1, 1, 0.75, and 0.5 cm2 were connected in series within the same furnace at 800 C and a gas environment of 97% H2 and 3% H2O. A current of 0.75 A was run through three of the cells, resulting in current densities of 0.75, 1.0, and 1.5 A/cm2, while one was maintained with no current. The life test lasted for 500 h, and the microstructure was observed at 0, 200, and 500 hours.
Figure 1 shows the microstructures observed at the highest current density by polished cross-sectional SEM and FIB-polished sections under conditions that provided Ni/YSZ contrast. Microstructural degradation had occurred by 200 h and became immense at 500 h, due to high current density in these reducing conditions. By 200 hours, grain boundaries become enriched with Ni, likely due to the formation of Ni-Zr intermetallics in the ultra-low pO2 induced by local overpotential as reported by Chen[1] and Szasz[2]. Additionally, the electrode-electrolyte interface becomes nanoporous and a Ni enriched fracture is present ~2 μm into the electrolyte. By 500 hours, the Ni rich nanoporosity has progressed more than 10 μm into the electrolyte and created islands of large grains surrounded by Ni-rich deposits.
Electrochemical impedance spectroscopy measurements show a clear initial decrease in polarization resistance followed by an overall impedance increase by 200 hours. These correspond to the initial electrochemical boost from the production of a nanoporous structure, followed by the deactivation of areas of the cell due to the large fractures through the electrolyte.
[1] M. Chen et al., “Microstructural Degradation of Ni/YSZ Electrodes in Solid Oxide Electrolysis Cells under High Current,” J. Electrochem. Soc., vol. 160, no. 8, pp. F883–F891, 2013, doi: 10.1149/2.098308jes.
[2] J. Szász et al., “High-Resolution Studies on Nanoscaled Ni/YSZ Anodes,” Chem. Mater., vol. 29, no. 12, pp. 5113–5123, 2017, doi: 10.1021/acs.chemmater.7b00360.
Figure 1: Microstructural and electrochemical changes of a symmetric Ni-YSZ SOC undergoing 1.5 A/cm2 in reducing conditions at 0, 200, and 500 hours. Cathode is on the left in all images; anode is on the right. a, b, c) Backscatter electron imaging reveals destruction of the dense YSZ electrolyte over the lifetime of the experiment. Lines of brighter phases on the anode side of fractures are Ni deposits. d, e, f) Focused Ion Beam cross sections reveal nanoporosity forming in the first 10 μm from the cathode-electrolyte interface at 200 and 500 hours. Charging is evident as a result of curtaining from the nanoporous features in the electrolyte. g) Electrochemical impedance spectroscopy shows the initial decrease in resistance from 0 to 48 hours followed by increasing resistance due to microstructure evolution.

Figure 1