Issue 9, 2016

Thermodynamic and kinetic studies of LiNi0.5Co0.2Mn0.3O2 as a positive electrode material for Li-ion batteries using first principles

Abstract

Ni-rich Li-based layered Ni, Co, and Mn (NCM) materials have shown tremendous promise in recent years as positive electrode materials for Li-ion batteries. This is evident as companies developing batteries for electrical vehicles are currently commercializing these materials. Despite the considerable research performed on LiNiαCoβMnγO2 systems, we do not yet have a complete atomic level understanding of these materials. In this work we study the cationic ordering, thermodynamics, and diffusion kinetics of LiNi0.5Co0.2Mn0.3O2 (NCM-523). Initially, we show that cationic ordering can be predicted employing cheap atomistic simulations, instead of using expensive first-principles methods. Subsequently, we investigate the electrochemical, thermodynamic and kinetic properties of NCM-523 using density functional theory (DFT). Our results demonstrate the importance of including dispersion corrections to standard first principles functionals in order to correctly predict the lattice parameters of layered cathode materials. We also demonstrate that a careful choice of computational protocol is essential to reproduce the experimental intercalation potential trends observed in the LiNi0.5Co0.2Mn0.3O2 electrodes. Analysis of the electronic structure confirms an active role of Ni in the electrochemical redox process. Moreover, we confirm the experimental finding that on complete delithiation, this material remains in an O3 phase, unlike LiCoO2 and NCM-333. Finally, we study various pathways for the Li-ion diffusion in NCM-523, and pinpoint the preferred diffusion channel based on first principles simulations. Interestingly, we observe that the Li diffusion barrier in NCM-523 is lower than that in LiCoO2.

Graphical abstract: Thermodynamic and kinetic studies of LiNi0.5Co0.2Mn0.3O2 as a positive electrode material for Li-ion batteries using first principles

Supplementary files

Article information

Article type
Paper
Submitted
19 十一月 2015
Accepted
25 一月 2016
First published
02 二月 2016

Phys. Chem. Chem. Phys., 2016,18, 6799-6812

Author version available

Thermodynamic and kinetic studies of LiNi0.5Co0.2Mn0.3O2 as a positive electrode material for Li-ion batteries using first principles

M. Dixit, M. Kosa, O. S. Lavi, B. Markovsky, D. Aurbach and D. T. Major, Phys. Chem. Chem. Phys., 2016, 18, 6799 DOI: 10.1039/C5CP07128C

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements