The Composition of Oxygen Functionals Groups at the Surface of Carbon-Based Graphitic Anode

In lithium-ion batteries (LIBs), the quality of a solid electrolyte interphase (SEI) that forms at the electrode/electrolyte interface substantially affects the stability and lifetime of the devices. One of the major determinants of the morphology and properties of SEI is the surface structure and composition of the graphitic anode used. The presence of oxygenated surface groups at the graphitic anode facilitates the formation of SEI at the interface that stabilizes LIBs. A series of DFT calculations reveal that at typical operating conditions (temperature, pH) of LIBs, the (1120) edge facet of graphite anode will be fully oxygenated, while the basal sites remain unsaturated. The oxygen functional groups at the edge sites are comprised of mostly hydroxyl and ketonic groups, with carboxyl and carbonyl groups are present in small amounts. Furthermore, we observe transformation of carbonyl group into ketonic group in the presence of empty surface carbon sites, which further stabilize the graphite surface. Meanwhile, carboxyl groups are more stable when all surface sites within a carboxyl layer are all populated. On the contrary to the edge plane, a small amount of oxygen functional groups may be forced to adsorb on the basal surface upon application of an external potential.