Thermodynamic properties of LiNiO 2 , LiCoO 2 , and LiMnO 2 using density-functional theory

The formation energies of LiCoO , LiNiO and LiMnO were calculated using a combination of adequately selected Hess cycles and DFT computations. Several exchange-correlation functionals were tested and PBE for solids (PBEsol) turned out to be the most accurate. The enthalpies of formation at 0 K are -...

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Published in:Physical chemistry chemical physics : PCCP 2023-08, Vol.25 (30), p.20641-20656
Main Authors: Tosin Paese, Lucas, Zeller, Philippe, Chatain, Sylvie, Guéneau, Christine
Format: Article
Language:English
Subjects:
Chemical Sciences
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Summary:The formation energies of LiCoO , LiNiO and LiMnO were calculated using a combination of adequately selected Hess cycles and DFT computations. Several exchange-correlation functionals were tested and PBE for solids (PBEsol) turned out to be the most accurate. The enthalpies of formation at 0 K are -168.0 kJ mol at for LiCoO , -173.2 kJ mol at for LiNiO , -209.9 kJ mol at for -LiMnO and -208.8 kJ mol at for r-LiMnO . In comparison to experimental formation energy data, a difference of 1.6 and 0.01 kJ mol at was obtained for LiCoO and LiMnO , respectively. By contrast, a much larger discrepancy, around 24 kJ mol at , was obtained for LiNiO and confirmed by using an additional and independent Hess cycle. The influence of slight crystallographic distortions associated with magnetism and/or the Jahn-Teller effect on energy was carefully searched for and taken into account, as well as corrections arising from vibrational contributions. Hence, these results should motivate future measurements of the thermodynamic properties of LiNiO , which are currently scarce. Vibrational contributions to the structural and energetic properties were computed within the harmonic and the quasi-harmonic approximations. The LiCoO heat capacity at constant pressure is in excellent agreement with experimental data, with a difference of only 3.3% at 300 K. In the case of LiNiO the difference reaches 17% at 300 K, which could also motivate further investigation. The ( ) value for the orthorhombic phase -LiMnO , for which no previous data were available, was computed. Structural properties such as specific mass, bulk modulus and coefficient of thermal expansion are presented.
ISSN:1463-9076
1463-9084
DOI:10.1039/D3CP01771K