Oxygen Ion Conduction Property of Solid Oxide Membrane Based on Multi-scale Analysis
Authors: Ijichi Takumi , Nagashima Hiroki , Hartwell Alexander , Ahn Jeongmin , Tokumasu Takashi 
Published: September 2023

In recent years, various environmental problems such as rising temperature, droughts, and extreme weather events have become more serious in many parts of the world because of global warming. One of the causes of the global warming is an increase in emissions of greenhouse gases such as CO2, CH4, and N2O, those are emitted during a combustion of fossil fuels such as coal, oil, and natural gas in thermal power generation. As energy consumption accelerates year by year, the depletion of fossil fuels is also becoming an issue. Therefore, hydrogen energy is attracting attention. Hydrogen is known as a clean energy because it reacts with oxygen to produce only water and chemical energy.
Fuel cells are attracting attention as a new power generation device that produces electricity from hydrogen energy. Fuel cells generate electricity directly through chemical reactions, resulting in minimal power generation loss from energy conversion. Solid oxide fuel cells (SOFC), in which solid oxide electrolyte membrane (SOEM) is used as the electrolyte membrane, have particularly high-power generation efficiency. On the other hand, the operating temperature of SOFCs is extremely high (over 1000 K), which accelerates degradation of SOEM. Therefore, it is necessary to lower the operating temperature from high to medium (about 700 K) while maintaining high power generation efficiency.
To solve this problem, we focus on dual-phasing and nano-structuring of SOEMs. Previous studies of SOEM have shown that dual-phase membranes have better ion transport performance than a single-phase membrane. For example, a dual-phase SOEM is composed of SSC (SrSc0.1Co0.9O3-d) with perovskite structure and SDC (Sm0.2Ce0.8O2-d) with fluorite structure. One the other hand, nano-structuring are nano-thin film and nano-crystalline. Nano-thin film is a method of forming an electrolyte film of several μm by layering nano-films of several nm in size. Nano-crystalline is a method to reduce a crystal size to several tens of nanometers. By these nano structures, the resistance of ion conduction is reduced, and ion conductivity is improved.
However, the number of interfaces in dual-phase SOEM and nano structured membrane is expected to increase. Previous studies have reported a decrease in ion conductivity near the interface between different structures of membrane. This decrease in ion conductivity at the interface is caused by an increase in the energy barrier as the conduction path passes through the interface. The correlation between the reduction of ion conductivity and nano structures in membrane has not been clarified clearly.
In this study, we analyze the mechanism of oxygen ion conductivity reduction near the interface by numerical simulations. Molecular simulations are performed to build up information by multi-scale analysis. Specifically, density functional theory (DFT), molecular dynamics (MD), and kinetic Monte Carlo (kMC) are performed in a bottom-up manner. First, MD simulations were performed using a potential model constructed from the energy states in the atomic arrangement at the interface obtained by DFT. We analyzed the ion conductivity at the interface and its crystal size dependence. We also create a hopping model of oxygen ions moving from site to site for kMC simulations. Next, kMC simulations are performed to analyze the oxygen ion conductivity in the dual-phase SOEM including interface, on a time and spatial scale similar to that of a real SOEMs.
In this presentation, we report on the results of MD simulation. A dual-phase SOEM model consisting of SSC and SDC was used as the simulation model (Fig.1(a)). The diffusion coefficient of oxygen ions was obtained as an indicator of ionic conductivity. Because the ionic conductivity is determined by the balance between the energy barrier of the conduction path and the kinetic energy of the ions involved in ionic conduction. In this study, the activation energy for the diffusion was calculated as the energy barrier. The activation energy was estimated from Arrhenius relation of diffusion coefficient. The number of unit cells in the dual-phase SOEM model was varied to change the crystal size. As a result, both the diffusion coefficient and activation energy increase as the crystal size of SSC increases. On the other hand, as the crystal size of SDC increases, although the diffusion coefficient decreases, the activation energy increases (Fig.1(b)). These results show the dependence of the diffusion coefficient and activation energy on the crystal size in a dual-phase SOEM.

Figure 1