Oxygen reduction by lithium on model carbon and oxidized carbon structures

Xu, Ye; Shelton, Jr, William Allison

doi:10.1149/1.3625620

Oxygen reduction by lithium on model carbon and oxidized carbon structures

Journal Article · Fri Dec 31 23:00:00 EST 2010 · Journal of the Electrochemical Society

DOI:https://doi.org/10.1149/1.3625620· OSTI ID:1022657

Xu, Ye ^[1]; Shelton, Jr, William Allison ^[1]

ORNL

Li-air batteries have attracted substantial interest for their high theoretical specific energies, but the oxygen reduction reaction by Li (Li-ORR) that occurs at the carbon cathode remains poorly understood. Periodic density functional theory calculations have been performed to examine the Li-ORR on several model carbon structures, including the graphite(0001) basal plane, the (8,0) single-wall nanotube, the armchair-type edge, and a di-vacancy in the basal plane. The inertness of the basal plane limits the reversible potential of O{sub 2} reduction to 1.1 V, and slightly higher to 1.2 V on the curved nanotube. The armchair edge and di-vacancy are highly reactive and significantly oxidized at ambient conditions to various CO{sub x} groups, which are reduced by Li via redox mechanisms at 1.2-1.4 V. These CO{sub x} groups can also catalyze O{sub 2} reduction at up to 2.3 V (an overpotential of 0.4 V vs. the calculated equilibrium potential for bulk Li{sub 2}O{sub 2} formation) by chelating and stabilizing the LiO{sub 2} intermediate. The Li-ORR on graphitic carbon, if via concerted Li{sup +}/e{sup -} transfer and involving carbon, lithium, and oxygen only, is therefore expected to initiate with the smallest overpotential at under-coordinated carbon centers that are oxidized at ambient conditions.

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); Oak Ridge National Laboratory (ORNL)

Sponsoring Organization:: DOE Office of Science; ORNL LDRD Director's R&D

DOE Contract Number:: AC05-00OR22725

OSTI ID:: 1022657

Journal Information:: Journal of the Electrochemical Society, Journal Name: Journal of the Electrochemical Society Journal Issue: 10 Vol. 158; ISSN 0013-4651

Country of Publication:: United States

Language:: English

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