New Family of Interstitial Oxygen Ion Conductor Discovered By High-Throughput Computational Screening
Authors: Meng Jun , Sheikh Md Sariful , Jacobs Ryan , Liu Jian , Nachlas William O. , Morgan Dane 
Published: September 2023

Discovery and design of highly efficient oxygen-active materials which react with, absorb, and transport oxygen is essential for fuel cells and related applications. Currently, the predominant families of oxygen-active materials used in commercial devices are perovskites and fluorites, which diffuse oxygen via a vacancy mechanism and only have adequate oxygen diffusivity and surface exchange at high temperatures (e.g., ~800 ˚C), impeding their use at lower temperatures desirable for more cost-effective and long-lasting device operation. The development of alternative electrolyte/electrode materials with high oxygen ionic conductivity at low temperatures (e.g., room temperature to 400 °C) is of great interest. Interstitial oxygen ion conductors typically have significantly lower migration barriers than even state-of-the-art vacancy-mediated oxygen conductors, which can provide orders of magnitude kinetic enhancement at low temperatures. In addition, the interstitial oxygen defects typically become more thermodynamically favorable as the temperature is lowered, potentially providing an additional boost to the oxygen conductivity at low temperatures from a higher mediating defect concentration. The synergistic combination of low migration barriers and thermodynamically favorable interstitial oxygen content at low temperatures provides the tantalizing possibility that interstitial oxygen conductors may lead to transformative performance improvements in oxygen-active materials.

In this work, we developed an approach to discover new interstitial-mediated oxygen conductors by performing high-throughput computational screening of the 34k oxide materials from the Materials Project database and discovered a new structural family of interstitial oxygen diffusers, perrierite-type oxide La4Mn5Si4O22+
𝜹 (LMS). We used a hierarchy of screening criteria including the geometric free space, thermodynamic stability, synthesizability, redox-active elements, and presence of short diffusion pathways. This approach, based largely on simple, physically intuitive properties, quickly winnowed the field of 34k oxides down to just 345 oxides, an approximate 99% reduction in the search space considered, with essentially no significant computational cost. From this reduced set of promising materials, ab initio simulations were performed to calculate the interstitial oxygen formation energy and migration energy. Our screening has yielded several material families to date, among which the A4B5C4O22+
𝜹, with La4Mn5Si4O22+
𝜹 (LMS) as a representative material, was selected for investigation with higher-fidelity DFT hybrid functional calculations and experimental validations. The calculated formation energy of interstitial oxygen is -0.11 eV at a concentration of 2.3% under air condition, indicating that LMS

is predicted to be oxygen hyperstoichiometric with an expected composition of La4Mn5Si4O22+0.5 in air. Two separate interstitial and interstitialcy (“kick-out”) diffusion mechanisms are revealed by ab initio molecular dynamics (AIMD) simulation. For the interstitial diffusion pathway, the moves through the channel in between the zigzag-arranged sorosilicate Si2O7 groups, with a barrier of 0.69 eV. For the interstitialcy diffusion pathway, the moves along the corner-sharing Si2O7-MnO2-Si2O7 framework by kicking out the lattice oxygen, with a barrier of 0.74 eV. These results align well with the experimental findings of stable interstitial oxygen content and high oxygen mobility in LMS (Please see a separate poster from Md Sariful Sheikhfor experimental results). This work provides a systematic approach to screening a large number of prospective materials and opens a new avenue of finding promising interstitial oxide ion conducting materials for potential applications in a range of fast oxygen ion conduction-based technologies.