Structure and Stability of Lithium Superoxide Clusters and Relevance to Li-O2 Batteries.
The discharge mechanism of a Li-O2 battery involves lithium superoxide (LiO2) radicals. In this Letter, we have performed high-level quantum chemical calculations (G4MP2) to investigate the structure and stability of LiO2 clusters. The clusters have planar ring-shaped structures, high spins, and are thermodynamically more stable than LiO2 dimer. The computed energy barrier for disproportionation of the larger clusters is also significantly higher than the corresponding barrier in the LiO2 dimer (1.0 eV vs 0.5 eV). This means that disproportionation rate should be much slower if the reaction involves LiO2 clusters other than the dimer. As a result, the clusters may survive long enough to be incorporated into the growing discharge product. These results are discussed in terms of recent experimental studies of the electronic structure and morphology of the discharge products in Li-air batteries.
†Materials Science Division, Argonne National Laboratory, Argonne, Illinois 60439, United States.
Ujjal
U
Das
†Materials Science Division, Argonne National Laboratory, Argonne, Illinois 60439, United States.
Kah Chun
KC
Lau
‡Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, Illinois 60439, United States.
Paul C
PC
Redfern
†Materials Science Division, Argonne National Laboratory, Argonne, Illinois 60439, United States.|§Center for Nanoscale Materials, Argonne National Laboratory, Argonne, Illinois 60439, United States.
Larry A
LA
Curtiss
G4MP2; disproportionation kinetics; high spin clusters; nucleation and growth