Replacement of Cobalt in Lithium-Rich Layered Oxides by n-Doping: A DFT Study

The replacement of cobalt in the lattice of lithium-rich layered oxides (LRLO) is mandatory to improve their environmental benignity and reduce costs. In this study, we analyze the impact of the cobalt removal from the trigonal LRLO lattice on the structural, thermodynamic, and electronic properties...

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Autores principales:	Mariarosaria Tuccillo, Lorenzo Mei, Oriele Palumbo, Ana Belén Muñoz-García, Michele Pavone, Annalisa Paolone, Sergio Brutti
Formato:	article
Lenguaje:	EN
Publicado:	MDPI AG 2021
Materias:	density functional theory Li-ion batteries positive electrodes lithium-rich layered oxides cobalt Technology T Engineering (General). Civil engineering (General) TA1-2040 Biology (General) QH301-705.5 Physics QC1-999 Chemistry QD1-999
Acceso en línea:	https://doaj.org/article/551264d8a5884e29a0e1c4b20f98d963
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spelling	oai:doaj.org-article:551264d8a5884e29a0e1c4b20f98d9632021-11-25T16:31:13ZReplacement of Cobalt in Lithium-Rich Layered Oxides by n-Doping: A DFT Study10.3390/app1122105452076-3417https://doaj.org/article/551264d8a5884e29a0e1c4b20f98d9632021-11-01T00:00:00Zhttps://www.mdpi.com/2076-3417/11/22/10545https://doaj.org/toc/2076-3417The replacement of cobalt in the lattice of lithium-rich layered oxides (LRLO) is mandatory to improve their environmental benignity and reduce costs. In this study, we analyze the impact of the cobalt removal from the trigonal LRLO lattice on the structural, thermodynamic, and electronic properties of this material through density functional theory calculations. To mimic disorder in the transition metal layers, we exploited the special quasi-random structure approach on selected supercells. The cobalt removal was modeled by the simultaneous substitution with Mn/Ni, thus leading to a p-doping in the lattice. Our results show that cobalt removal induces (a) larger cell volumes, originating from expanded distances among stacked planes; (b) a parallel increase of the layer buckling; (c) an increase of the electronic disorder and of the concentration of Jahn–Teller defects; and (d) an increase of the thermodynamic stability of the phase. Overall p-doping appears as a balanced strategy to remove cobalt from LRLO without massively deteriorating the structural integrity and the electronic properties of LRLO.Mariarosaria TuccilloLorenzo MeiOriele PalumboAna Belén Muñoz-GarcíaMichele PavoneAnnalisa PaoloneSergio BruttiMDPI AGarticledensity functional theoryLi-ion batteriespositive electrodeslithium-rich layered oxidescobaltTechnologyTEngineering (General). Civil engineering (General)TA1-2040Biology (General)QH301-705.5PhysicsQC1-999ChemistryQD1-999ENApplied Sciences, Vol 11, Iss 10545, p 10545 (2021)
institution	DOAJ
collection	DOAJ
language	EN
topic	density functional theory Li-ion batteries positive electrodes lithium-rich layered oxides cobalt Technology T Engineering (General). Civil engineering (General) TA1-2040 Biology (General) QH301-705.5 Physics QC1-999 Chemistry QD1-999
spellingShingle	density functional theory Li-ion batteries positive electrodes lithium-rich layered oxides cobalt Technology T Engineering (General). Civil engineering (General) TA1-2040 Biology (General) QH301-705.5 Physics QC1-999 Chemistry QD1-999 Mariarosaria Tuccillo Lorenzo Mei Oriele Palumbo Ana Belén Muñoz-García Michele Pavone Annalisa Paolone Sergio Brutti Replacement of Cobalt in Lithium-Rich Layered Oxides by n-Doping: A DFT Study
description	The replacement of cobalt in the lattice of lithium-rich layered oxides (LRLO) is mandatory to improve their environmental benignity and reduce costs. In this study, we analyze the impact of the cobalt removal from the trigonal LRLO lattice on the structural, thermodynamic, and electronic properties of this material through density functional theory calculations. To mimic disorder in the transition metal layers, we exploited the special quasi-random structure approach on selected supercells. The cobalt removal was modeled by the simultaneous substitution with Mn/Ni, thus leading to a p-doping in the lattice. Our results show that cobalt removal induces (a) larger cell volumes, originating from expanded distances among stacked planes; (b) a parallel increase of the layer buckling; (c) an increase of the electronic disorder and of the concentration of Jahn–Teller defects; and (d) an increase of the thermodynamic stability of the phase. Overall p-doping appears as a balanced strategy to remove cobalt from LRLO without massively deteriorating the structural integrity and the electronic properties of LRLO.
format	article
author	Mariarosaria Tuccillo Lorenzo Mei Oriele Palumbo Ana Belén Muñoz-García Michele Pavone Annalisa Paolone Sergio Brutti
author_facet	Mariarosaria Tuccillo Lorenzo Mei Oriele Palumbo Ana Belén Muñoz-García Michele Pavone Annalisa Paolone Sergio Brutti
author_sort	Mariarosaria Tuccillo
title	Replacement of Cobalt in Lithium-Rich Layered Oxides by n-Doping: A DFT Study
title_short	Replacement of Cobalt in Lithium-Rich Layered Oxides by n-Doping: A DFT Study
title_full	Replacement of Cobalt in Lithium-Rich Layered Oxides by n-Doping: A DFT Study
title_fullStr	Replacement of Cobalt in Lithium-Rich Layered Oxides by n-Doping: A DFT Study
title_full_unstemmed	Replacement of Cobalt in Lithium-Rich Layered Oxides by n-Doping: A DFT Study
title_sort	replacement of cobalt in lithium-rich layered oxides by n-doping: a dft study
publisher	MDPI AG
publishDate	2021
url	https://doaj.org/article/551264d8a5884e29a0e1c4b20f98d963
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Replacement of Cobalt in Lithium-Rich Layered Oxides by n-Doping: A DFT Study

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