Thermochemistry of the Cu2Se–In2Se3 system

• Published in: Journal of alloys and compounds 2014-08, Vol.604, p.363-372
• Main Authors: Ider, M., Pankajavalli, R., Zhuang, W., Shen, J.Y., Anderson, T.J.
• Format: Article
• Language: English
• Subjects: Chemistry; Copper indium di-selenide; Electrochemistry; Exact sciences and technology; General and physical chemistry; Gibbs energy of formation; Phase diagram; Solid electrolyte EMF measurements; System Cu2Se–In2Se3; Thermodynamic assessment
• ISSN: 0925-8388; 1873-4669
• DOI: 10.1016/j.jallcom.2014.03.129

•Solid state EMF experiments were employed to obtain Gibbs energy data of CuInSe2.•The phase diagram data in the Cu2Se–In2Se3 pseudo-binary system were assessed.•ΔGf∘ CuInSe2 (α)±0.0003=0.0051T (K)−220.92kJ/mol (949–1044K) was obtained.•ΔGf∘ CuInSe2 (δ)±0.0004=−0.0043T (K)−210.92kJ/mol (1055–1150K) was obtained.•Ttrans and, ΔHtrans∘ for α to δ-CuInSe2 were determined to be 1064K and 10.0kJ/mol. Solid state electrochemical cells were employed to obtain standard Gibbs energy of formation of CuInSe2 as well as the temperature and enthalpy of the α to δ-CuInSe2 transformation in the Cu2Se–In2Se3 pseudo-binary system. The reversible EMF data of the following solid-state electrochemical cell were measured:Pt,In(l),In2O3(s)‖YSZ‖In2O3(s),Cu2Se(s),Cu(s),CuInSe2(αorδ),C,PtCell IThe calculated standard molar Gibbs energy of formation of α and δ-CuInSe2 from measured data are given byΔGf∘CuInSe2(α)±0.0003=0.0051T(K)-220.92kJ/mol(949–1044K)ΔGf∘CuInSe2(δ)±0.0004=-0.0043T(K)-210.92kJ/mol(1055–1150K)The α to δ phase transition temperature Ttrans and the enthalpy of transition ΔHtrans∘ for CuInSe2 were determined to be 1064K and 10.0kJ/mol respectively. ΔStrans∘ was calculated as 9.4J/molK. The thermodynamic and phase diagram data in the Cu2Se–In2Se3 pseudo-binary system were critically assessed. A self consistent set of thermochemistry and phase diagram data was obtained with the help of measured data. The liquid phase along the Cu2Se–In2Se3 pseudo-binary was calculated with the Redlich–Kister model. The β-Cu1In3Se5 and γ-Cu1In5Se8 phases were represented by the sub-regular model. The ordered non-stoichiometric α-CuInSe2 and δ-CuInSe2 phases were modeled by using a three-sublattice formalism. The calculated phase diagram and thermochemical data show reasonable agreement.