Stability and Performance of Oxygen Electrodes for Reversible Solid Oxide Cells

Public Deposited

Worldwide, governments are beginning to take action to reduce anthropogenic CO2 emissions in order to mitigate the extent of global climate change. The largest fraction of global CO2 emission comes from electrical power generation, which is rapidly being converted to wind and solar installations. The intermittent nature of renewable resources requires that large scale energy storage be implemented to ensure grid stability. Pumped hydro storage is currently the only technology available for large scale energy storage; however, pumped hydro remains geographically confined and susceptible to seasonal fluctuations and offers limited discharge hours. Recent system level models predict that reversible solid oxide cells may be a competitive solution, but two key advancements are required to realize the technology: low cell resistance (<0.2 Ω•cm2 at <650 °C), particularly low polarization resistance at the oxygen electrode, and low degradation rate (<0.5%/khr for 50,000 hours). The oxygen electrode is typically the largest contributor to the total cell resistance, and when a cell is operated in electrolysis the oxygen electrode is known to degrade quickly. This work focuses on both aspects of the oxygen electrode. ]A Pr2NiO4 based electrode is developed that has improved phase stability and good polarization resistance (~0.1 Ω•cm2 at 650 °C). The electrode is prepared by wet chemical impregnation (infiltration) of Pr2NiO4 precursors into a La0.9Sr0.1Ga0.8Mg0.2O3 scaffold. Electrochemical data for a number cells is presented and the number of infiltrations is optimized. Preliminary life tests and x-ray data are presented. Pressurization of the oxygen electrode is predicted to decrease its polarization resistance and pressurization of the reversible solid oxide cell system is desirable to achieve high round-trip efficiency. The electrochemical performance of mixed electronic-ionic conducting electrodes has not been reported above 1 atm. Four candidate electrodes are examined under pressurization up to 10 atm: Pr2NiO4 infiltrated La0.9Sr0.1Ga0.8Mg0.2O3, Sm0.5Sr0.5CoO3 infiltrated Ce0.9Gd0.1O2, single phase La0.6Sr0.4Co0.2Fe0.8O3, and single phase Nd2NiO4. The role of the ion conduction mechanism (vacancy or interstitial) is explored in relation to the decrease in polarization resistance with increased pressure. Current switched life-tests designed to emulate reversible solid oxide cell operating conditions were performed for a range of current densities and overpotentials on three candidate systems: composite La0.7Sr0.3MnO3-Zr0.84Y0.16O2, single phase La0.6Sr0.4Co0.2Fe0.8O3, and La2NiO4 infiltrated La0.9Sr0.1Ga0.8Mg0.2O3. The degradation mode of each system is determined by impedance spectroscopy and post-test microstructural analysis. Operating regions of improved stability are identified for each system based on the measured degradation rates. Overpotential is determined to be the major controlling factor in La0.7Sr0.3MnO3-Zr0.84Y0.16O2. Analysis and modeling for predicting the long term degradation of an infiltrated electrode is presented. Coarsening of the nanoscale features is thought to be the main contributor to degradation under annealing for infiltrated electrodes and so a combined electrochemical –coarsening model is presented to understand the limitations of such an electrode. The model is fit to prior results to better understand the trade-off between coarsening rate and initial good performance. A figure of merit is presented for selecting materials for infiltration that takes into account the coarsening behavior.

Last modified
  • 02/19/2018
Date created
Resource type
Rights statement