Structural and electronic properties of bulk Li₂O₂: first-principles simulations based on numerical atomic orbitals

The development of advanced materials with high specific energy is crucial for enabling sustainable energy storage solutions, particularly in applications such as lithium-air batteries. Lithium peroxide (Li₂O₂) is a key discharge product in non-aqueous lithium-air systems, where its structural and electronic properties significantly influence battery performance. In this work, we investigate the atomic structure, electronic band structure, and Wannier functions of bulk Li₂O₂using density functional theory. The performance of different basis sets of numerical atomic orbitals is compared with respect to converged plane-wave basis results. We analyse the material's ionic characteristics, the formation of molecular orbitals in oxygen dimers, and the band gap discrepancies between various computational approaches. Furthermore, we develop a localized Wannier basis to model electron-vibration interactions and explore their implications for polaron formation. Our findings provide a chemically intuitive framework for understanding electron-lattice coupling and offer a basis for constructing reduced models that accurately describe the dynamics of polarons in Li₂O₂. These insights contribute to the broader goal of improving energy storage technologies and advancing the field of materials design.