Knowledge of the precise molecular mechanisms during the discharge and recharge processes in the lithium-air battery is critical for achieving desired improvements in specific capacity, current density, and cyclability. The initial oxygen reduction product formed in the presence of Li(+) ions is lithium superoxide LiO(2). In this study, we report the computed structures and thermodynamic parameters of LiO(2) dimerization in the gas phase, which enables us to provide a baseline for the reaction free energy profile of the subsequent disproportionation of (LiO(2))(2) to lithium peroxide Li(2)O(2) and O(2). Our calculations identified several low-lying (LiO(2))(2) dimers, with the singlet bipyramidal structure giving IR bands that are consistent with the characteristic IR vibration frequencies of (LiO(2))(2) in the oxygen matrix at T = 15-40 K. The activation barrier for (LiO(2))(2) = Li(2)O(2)+O(2) is 10.9 kcal/mol at the UCCSD(T)/CBS level (T = 298 K), suggesting that in the gas phase LiO(2) and its aggregates could only be observed at low temperatures.

Stability of Lithium Superoxide LiO(2) in the Gas Phase: Computational Study of Dimerization and Disproportionation Reactions / V. S., Bryantsev; M., Blanco; Faglioni, Francesco. - In: JOURNAL OF PHYSICAL CHEMISTRY. A, MOLECULES, SPECTROSCOPY, KINETICS, ENVIRONMENT, & GENERAL THEORY. - ISSN 1089-5639. - STAMPA. - 114:(2010), pp. 8165-8169. [10.1021/jp1047584]

Stability of Lithium Superoxide LiO(2) in the Gas Phase: Computational Study of Dimerization and Disproportionation Reactions

FAGLIONI, Francesco
2010

Abstract

Knowledge of the precise molecular mechanisms during the discharge and recharge processes in the lithium-air battery is critical for achieving desired improvements in specific capacity, current density, and cyclability. The initial oxygen reduction product formed in the presence of Li(+) ions is lithium superoxide LiO(2). In this study, we report the computed structures and thermodynamic parameters of LiO(2) dimerization in the gas phase, which enables us to provide a baseline for the reaction free energy profile of the subsequent disproportionation of (LiO(2))(2) to lithium peroxide Li(2)O(2) and O(2). Our calculations identified several low-lying (LiO(2))(2) dimers, with the singlet bipyramidal structure giving IR bands that are consistent with the characteristic IR vibration frequencies of (LiO(2))(2) in the oxygen matrix at T = 15-40 K. The activation barrier for (LiO(2))(2) = Li(2)O(2)+O(2) is 10.9 kcal/mol at the UCCSD(T)/CBS level (T = 298 K), suggesting that in the gas phase LiO(2) and its aggregates could only be observed at low temperatures.
2010
114
8165
8169
Stability of Lithium Superoxide LiO(2) in the Gas Phase: Computational Study of Dimerization and Disproportionation Reactions / V. S., Bryantsev; M., Blanco; Faglioni, Francesco. - In: JOURNAL OF PHYSICAL CHEMISTRY. A, MOLECULES, SPECTROSCOPY, KINETICS, ENVIRONMENT, & GENERAL THEORY. - ISSN 1089-5639. - STAMPA. - 114:(2010), pp. 8165-8169. [10.1021/jp1047584]
V. S., Bryantsev; M., Blanco; Faglioni, Francesco
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11380/708757
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