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Supplemental Literature Review: Section III

Li-O (Lithium-Oxygen) H. Okamoto

[Massalski2] reported the existence of Li2O, Li3O2, bLiO, aLiO, and LiO2, in the Li-O system, but did not show the Li-O phase diagram. Earlier, [1968Kon] reported the Li2O liquidus of the Li-O phase diagram in a narrow composition range from 0 to 0.7 at.% Li. [1960Hof], [1968Che], and [1979Yon] also reported the liquidus data. [1992San] reviewed these reports and preferred the result of [1979Yon]. The phase diagram was shown in terms of log(at.% O) versus 1000/T(K). The existence of Li3O2 and LiO2 in the stable state was questioned. Figure 1 shows the Li-O phase diagram at 1 bar total pressure calculated by [2011Cha]. The melting point of Li2O was adopted from [1983Ort]. The decomposition temperature of LiO was derived from several sources in the literature. The calculated Li2O liquidus agreed well with the experimental data shown in [1992San].

References 1960Hof: E.E. Hoffman, The Solubility of O and N in Li and Methods of Li Purification, U.S. Atomic Energy Commission Report ORNL-2894, 1960, 24 pp 1968Che: V.I. Cheburkov and A.N. Rozanov, Reaction Kinetics of Molten Li with O and N, Metallovd. Chist. Metal., 1968, 7, p 168-173, in Russian 1968Kon: E.E. Konovalov, N.I. Seliverstov, and V.P. Emel’yanov, Solubility of Oxygen and Chlorine in Liquid Lithium, Russ. Metall., 1968, (3), p 77-78 1979Yon: R.M. Yonko, V.A. Moroni, J.E. Strain, and J.H. Devan, A Determination of the Solubility of Li2O in Liquid Li by Fast Neutron Activation, J. Nucl. Mater., 1979, 79(2), p 354-362 1983Ort: M.S. Ortman and E.M. Larsen, Preparation, Characterization, and Melting Point of High-Purity Lithium Oxide, J. Am. Ceram. Soc., 1983, 66(9), p 645-648 1992San: J. Sangster and A.D. Pelton, The Li-O (LithiumOxygen) System, J. Phase Equilib., 1992, 13(3), p 296-299 2011Cha: K. Chang and B. Hallstedt, Thermodynamic Assessment of the Li-O System, CALPHAD, 2011, 35, p 160-164

Weight Percent Oxxygen 0 10 20

30

40

2500

50

60

70

80

90

100

2400°C

G

2000

1500

1438°C

1342°C L

1000

500 340°C

180.6°C

(βLi)

0 0

Li

10

20

30

40

50

60

70

80

Atomic Percent Oxygen

90

100

O

Fig. 1 Li-O phase diagram [2011Cha]

Journal of Phase Equilibria and Diffusion Vol. 34 No. 2 2013

169