Abstract
Stoichiometric (Li2O2)n clusters (n = 1–6) were systematically studied by density functional theory calculations with hybrid B3LYP functional. The most stable structures of these clusters are triplet except for the Li2O2 monomer. In the Li2O2 monomer, the closed shell singlet is strongly favored. There are superoxide-like characteristics in terms of bond lengths and spin in the stoichiometric peroxide lithium clusters, which may have implications for the formation and decomposition of peroxide lithium in Li–O2 batteries. Furthermore, the growth process of the lowest energy structures of (Li2O2)n clusters is “ring-like” (n = 2) → “rectangle-like” (n = 3,4) → “Y-like” (n = 5) → “disc-like” (n = 6) feature, this growth pattern is in good agreement with the experimental observation at the initial phase of discharge in the Li–O2 battery. In addition, the values of energy gaps for the (Li2O2)n clusters are much smaller than the band gap of bulk phase, and thus the (Li2O2)n cluster can enhance the electron conductivity in the peroxide lithium. The frontier molecular orbitals analysis indicates that there are π* antibonding on the surface of (Li2O2)n clusters, making their structures more stable. Finally, the PES of (Li2O2)n clusters have been simulated, we hope that our simulated PES can be compared with future experimental data.
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.