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Open AccessArticle

Analysis of the Phase Stability of LiMO2 Layered Oxides (M = Co, Mn, Ni)

CNR-ISC, U.O.S. La Sapienza, Piazzale A. Moro 5, 00185 Rome, Italy
Department of Chemical Sciences and Department of Physics E. Pancini, University of Naples Federico II, Via Cintia 21, 80126 Napoli, Italy
Department of Chemistry, University of Rome La Sapienza, Piazzale Aldo Moro 5, 00185 Rome, Italy
Author to whom correspondence should be addressed.
Crystals 2020, 10(6), 526;
Received: 27 April 2020 / Revised: 4 June 2020 / Accepted: 8 June 2020 / Published: 20 June 2020
Transition-metal (TM) layered oxides have been attracting enormous interests in recent decades because of their excellent functional properties as positive electrode materials in lithium-ion batteries. In particular LiCoO2 (LCO), LiNiO2 (LNO) and LiMnO2 (LMO) are the structural prototypes of a large family of complex compounds with similar layered structures incorporating mixtures of transition metals. Here, we present a comparative study on the phase stability of LCO, LMO and LNO by means of first-principles calculations, considering three different lattices for all oxides, i.e., rhombohedral (hR12), monoclinic (mC8) and orthorhombic (oP8). We provide a detailed analysis—at the same level of theory—on geometry, electronic and magnetic structures for all the three systems in their competitive structural arrangements. In particular, we report the thermodynamics of formation for all ground state and metastable phases of the three compounds for the first time. The final Gibbs Energy of Formation values at 298 K from elements are: LCO(hR12) −672 ± 8 kJ mol−1; LCO(mC8) −655 ± 8 kJ mol−1; LCO(oP8) −607 ± 8 kJ mol−1; LNO(hR12) −548 ± 8 kJ mol−1; LNO(mC8) −557 ± 8 kJ mol−1; LNO(oP8) −548 ± 8 kJ mol−1; LMO(hR12) −765 ± 10 kJ mol−1; LMO(mC8) −779 ± 10 kJ mol−1; LMO(oP8) −780 ± 10 kJ mol−1. These values are of fundamental importance for the implementation of reliable multi-phase thermodynamic modelling of complex multi-TM layered oxide systems and for the understanding of thermodynamically driven structural phase degradations in real applications such as lithium-ion batteries. View Full-Text
Keywords: DFT; layered phases; Li-ion batteries; positive electrode materials; phase stability DFT; layered phases; Li-ion batteries; positive electrode materials; phase stability
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Tuccillo, M.; Palumbo, O.; Pavone, M.; Muñoz-García, A.B.; Paolone, A.; Brutti, S. Analysis of the Phase Stability of LiMO2 Layered Oxides (M = Co, Mn, Ni). Crystals 2020, 10, 526.

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